CN1425018A - Novel chromophores for polymeric thin films and optical waveguide and devices comprising the same - Google Patents

Novel chromophores for polymeric thin films and optical waveguide and devices comprising the same Download PDF

Info

Publication number
CN1425018A
CN1425018A CN 01808356 CN01808356A CN1425018A CN 1425018 A CN1425018 A CN 1425018A CN 01808356 CN01808356 CN 01808356 CN 01808356 A CN01808356 A CN 01808356A CN 1425018 A CN1425018 A CN 1425018A
Authority
CN
China
Prior art keywords
replacement
unsubstituted
compound
group
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 01808356
Other languages
Chinese (zh)
Inventor
M·何
T·M·莱斯利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/595,221 external-priority patent/US6584266B1/en
Application filed by Corning Inc filed Critical Corning Inc
Publication of CN1425018A publication Critical patent/CN1425018A/en
Pending legal-status Critical Current

Links

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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3611—Organic materials containing Nitrogen
    • G02F1/3612—Heterocycles having N as heteroatom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3613—Organic materials containing Sulfur
    • G02F1/3614—Heterocycles having S as heteroatom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3616—Organic materials containing polymers having the non-linear optical group in the main chain
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035—Materials
    • G02B2006/12069—Organic material

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Furan Compounds (AREA)

Abstract

The present invention is directed to chromophores having novel electron withdrawing groups and novel bivalent cyclic bridges and to optical waveguides and optical devices having polymeric thin films which contain the novel chromophores.

Description

Be used for the novel chromophores of polymeric film and contain its optical waveguides and device
The cross reference of related application
The application requires the exercise question submitted on June 16th, 2000 U.S. Patent application 09/595 for " be used for the novel chromophores of polymeric film and contain its optical waveguides and device ", the exercise question of submitting on September 29th, 221 and 2000 is the right of priority of the U.S. Patent application 09/675,966 of " be used for the novel chromophores of polymeric film and contain its optical waveguides and device ".
Invention field
The present invention relates to can be used for the optical waveguides and the device that prepare the chromophore compound of waveguide medium polymeric film and contain this chromophore compound.
Background of invention
Have big secondary nonlinear organic be that polymeric material membrane combines the Laser Modulation that can be used in optowire and many other waveguide purposes and deflection, management information system with silica-based electronic circuit.In addition, mix the novel method of carrying out the real-time processing of light field by third-order nonlinearity such as degeneracy four ripples and can be used for multiple field, as optical communication and unicircuit manufacturing.The application of organic materials with big secondary and third-order nonlinearity in high-frequency applications just demonstrates difference with the bandwidth restriction of the conventional inorganic electrooptical material of present use very much when comparing.
Many optic response monomer and polymkeric substance that can be used for organic materials have now been developed.These organic materialss can be used for again in the above-mentioned wave guide applications.For example, all many polymer compositions that suitable nonlinear optical response can be provided have been described with reference to the United States Patent (USP) 5,044,725 that is incorporated among the application.For example, United States Patent (USP) 5,044,725 have described the preferred polymeric compositions that contains organic chromophore compound.This organic chromophore compound contains electron-donating group and electron-withdrawing group in two opposite endpoint of bridge construction (bridge).
In order to make polymer-based carbon electro-optical transducer and device, necessary synthesized high-performance, the organic chromophore compound of high μ β electric light.Be applicable to the electric light color development bridge construction compound of nonlinear optical organic purposes and generally be well known in the art for the synthetic method of electronic bridge structural compounds.Though reported some chromophore compounds in the document, but wherein many some problems of existence, sometimes even serious problem, as insoluble, photodegradation in thermolability, the polymkeric substance, show that in useful wavelength region wide absorption band and polarity show high double refraction when adjusting.
Recently, United States Patent (USP) 6,067,186 have disclosed the organic chromophore compound of a class.These chromophore compounds can make the sclerosis electro-optic polymer be applicable to electrooptic modulator and other devices, as optical switch.
Still there is at present demand to suitable electric light chromophore compound with better performance.
Summary of the invention
The present invention partly relates to, and for example, can be used as the compound of chromophore compound in optical waveguides and the optics film.These compounds are represented with general formula I:
Figure A0180835600101
In the formula:
D is an electron-donating group;
B comprises at least one divalence ring; With
R 2And R 3Respectively do for oneself and replace or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl and (CH 2) n-O-(CH 2) n, wherein n is 1-10.Perhaps R 2And R 3Optional from replacing or unsubstituted C 1-C 10Alkyl, prerequisite are to work as R 2And R 3All be selected from and replace or unsubstituted C 1-C 10During alkyl, satisfy following condition: R 2≠ R 3The preferred chromophore compound general formula I of the present invention ' expression: In the formula:
R 2And R 3Further feature be that their determine ring, wherein * represents spiro junction or expression chiral centre; Or R 2And R 3Respectively do for oneself and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.D and B have above-mentioned definition.
In another aspect of this invention, chromophore compound comprises the novel ring-type bridge construction that contains at least one divalence aromatic ring.Preferred compound of the present invention is represented with general formula I I: D is an electron-donating group in the formula; A is an electron-accepting group; K is O or S; R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S; Q is 1,2 or 3.
Other preferred compounds of the present invention are represented with general formula III:
Figure A0180835600112
D is an electron-donating group in the formula; A is an electron-accepting group; J is CH 2, O or S; R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S.
In other embodiment of the present invention, chromophore compound comprises novel ring-type bridge construction and the novel electron-withdrawing group that contains at least one divalence or conjugate ring structure (as aromatic ring).These compounds are generally represented with the structure of general formula I V:
Figure A0180835600113
D is an electron-donating group in the formula; K is O or S; R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S; Q is 1,2 or 3; R 2And R 3Respectively do for oneself and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.Perhaps, R 2And R 3Form the ring structure of ring structure or replacement together.The preferred compound of this embodiment uses the structure of general formula I V ' to represent: In the formula:
R 2And R 3Further characteristics be to determine ring, wherein * represents spiro junction or expression chiral centre.
Other useful compounds of the present invention are represented with general formula V:
Figure A0180835600122
D is an electron-donating group in the formula; J is CH 2, O or S; R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S; R 2And R 3Hydrogen, replacement or unsubstituted C respectively do for oneself 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.Perhaps, R 2And R 3Form the ring structure of ring structure or replacement together.The preferred compound of this embodiment uses the structure of general formula V ' to represent:
Figure A0180835600131
In the formula:
R 2And R 3Further characteristics be to determine ring, wherein * represents spiro junction or expression chiral centre.
The present invention also relates to comprise the optical waveguides of the thin film dielectrics of representing with general formula VI:
Figure A0180835600132
Or P and P ' are the main polymer chain structural units in the formula, and they can be identical link units or different link units, and C is a comonomer unit, and n is the integer greater than 0, and n ' is 0 or greater than 0 integer; S is the separation side group that straight chain length is about 2-12 atom.M is above-mentioned with general formula I, general formula I ', the compound of general formula I I, general formula III, general formula I V, general formula I V ', general formula V or general formula V ' expression.
Term " electron-donating group " uses with the free burial ground for the destitute with " electron donor ", and is meant when the conjugated electrons structure polarizes by the input electromagnetic energy, can increase the substituting group of the electron density of π-electron system.
Term " electron-withdrawing group " uses with the free burial ground for the destitute with " electron-accepting group " and " electron acceptor(EA) ", and is meant when the conjugated electrons structure polarizes by the input electromagnetic energy, can attract the electronegativity organic compound or the substituting group of electron density from π-electron system.
The used term " chromophore compound (chromophore) " of the application is meant the optical compounds that comprises electron-donating group and electron-withdrawing group on the end relatively of conjugated pi-electron system.
Term " ring-type bridge construction " is used to represent to be used for the bivalent cyclic structure of coupling electron-donating group and electron-withdrawing group.
The present invention also relates to comprise the optics of above-mentioned optical waveguides.
The description of the preferred embodiment for the present invention
The present invention partly relates to novel electric light chromophore compound.These chromophore compounds can be used for the nonlinear optical organic purposes, as are used for the polymeric film of optical waveguides and optics.These polymeric films for example are documented in United States Patent (USP) 5,044, and 725,4,795,664,5,247,042,5,196,509,4,810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.Every patent is all with reference to being incorporated among the application.
Chromophore compound of the present invention has some advantages of not finding in other known or commercially available chromophore compounds.For example, we find to introduce chiral centre, preferably introduce chiral centre at the electron acceptor moiety of molecule, better with the racemic mixture form, can improve the solvability of chromophore compound greatly.When we have found that solubleness improves, R 2And R 3Between structure or sense difference increase.For example, work as R 2And R 3In one be chain, when another is ring texture, or when one of them be short chain (in 3 carbon atoms), and another be long-chain (is C 4-C 18) time, we observe solvability obviously increases.In many cases, the solvability of increase can improve the non-linear of final material again.As everyone knows, introduce the solvability that chain alkyl can increase chromophore compound, and when the number of alkyl increased with size, solvability and massive material (block) are non-linear can be improved greatly all.Chromophore compound of the present invention has higher solvability than existing diformazan base class chromophore compound.
Though also have the factor that other help to improve performance, we find that a main difference between acceptor of the present invention and the existing acceptor is to have chiral centre in the acceptor of the present invention.As everyone knows, the physical properties of pure enantiomorph such as fusing point and different solubility are in racemic mixture.The several examples that had this difference.For example, the fusing point of homochiral (D) lycine is 210 ℃, and at room temperature solubleness is very big.The fusing point of its racemic modification is 170 ℃, and the solubleness that is considered in room temperature water is infinity.Also have, the fusing point of the pure enantiomorph of amygdalic acid is 133 ℃, and the fusing point of its racemic modification is 120 ℃.(R)-(+)-fusing point of mandelonitrile is 29 ℃, and its racemic modification at room temperature is an oily matter.
In concrete chemistry of the present invention, chiral centre does not form single chipal compounds, and forms the mixture of racemize enantiomorph.When chiral centre is introduced chromophore compound, improved its solubleness owing to the fusing point that has reduced chromophore compound.In fact, we have found that compound of the present invention is easy to form vitreous solid, and do not form crystalline material.Though do not think bound by theoryly, we think that chemistry of the present invention has caused the nonlinear increase of mass polymer, and reason is to have introduced the racemize chiral centre in chromophore compound.
Electric light chromophore compound of the present invention has thermostability in 260-310 ℃ temperature range.These chromophore compounds also have high solubleness in the most frequently used organic solvent.Therefore, when chromophore compound of the present invention during, very useful as the object additive in most of waveguide polymeric films.In addition, (356 nanometers, dosage are 3 joules/centimetre at strong uv-radiation 2, irradiation reaches 13 minutes) under, the ultraviolet-visible-near-infrared spectrum of chromophore compound of the present invention does not change, and this shows that these chromophore compounds are that light is stable.These chromophore compounds also have adjustable absorption band in the place away from the proper communication wavelength.This is very important for reduce the light consumption in the communication wavelengths scope.Chromophore compound of the present invention has important three-dimensional design, and this can prevent chromophore compound-chromophore compound antiparallel stack.Because the replacement of flexible side-chains, the double refraction loss of chromophore compound of the present invention reduces greatly.In chromophore compounds more of the present invention, on the thiphene ring of bridging, there is unique regiospecificity to replace the position.This can allow electron acceptor(EA) more easily enter the conjugated pi-system of bridge construction, and makes molecular skeleton more smooth.In addition, some preferred chromophore compounds of the present invention have hydroxyl at the electron donor(ED) end, so that it is carried out the compatible organic and inorganic polymer reaction of hydroxyl, make soluble chromophore compound, polymkeric substance and multipolymer, also can be used for making high dissolubility " object " chromophore compound that is used for the host-guest purposes.
The present invention partly relates to the compound of the chromophore compound that can be used as the optical waveguides polymeric film.In preferred implementation of the present invention, these compounds contain the novel electron-withdrawing group that useful general formula I is represented: D is an electron-donating group in the formula.Preferred electron-donating group is United States Patent (USP) 5,044,725,4,795,664,5,247,042,5,196,509,4 for example, 810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.These patents are all with reference to being incorporated among the application.D better is selected from, but be not limited to by the phenyl ring of following group para-orientation: amino, alkylamino, dialkyl amido, dialkyl benzene amino, piperidino, 1-piperazinyl, 1-pyrrolidyl, amido, hydroxyl, thiol group, alkylthio, arylthio, alkoxyl group, aryloxy, acyloxy, alkyl, vinyl and 1,2,3,4-tetrahydric quinoline group etc.Most preferred electron-donating group is to replace or unsubstituted phenyl-N (CH 2CH 2OH) 2
B is the ring-type bridge construction that connects electron-withdrawing group and electron-donating group.B better is at least one divalence ring.Can be used as that the preferred divalence ring of ring-type bridge construction for example is documented in United States Patent (USP) 5,044,725,4,795,664,5 among the present invention, 247,042,5,196,509,4,810,338,4,936,645,5,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5, in 106,211 and 5,006,285.Each patent is all with reference to being incorporated among the application.The B ring can be aromatic ring or non-aromatic ring.B better is selected from following one group, but is not limited thereto:
Figure A0180835600162
R in the formula 4Be H, OH, C 1-C 10Alkyl, alkenyl, alkynyl group or halogen.R 4Also can be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S; Q is 1,2 or 3.
R 2And R 3Be selected from respectively, but be not limited to replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10." C 1-C 10" be meant C 1, C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10And the combination of these scopes.Preferably, work as R 2And R 3All be selected from and replace or unsubstituted C 1-C 10During alkyl, also satisfy following condition: R 2≠ R 3More preferably, R 2And R 3Determine a ring, wherein * represents spiro junction, or * represents chiral centre.
The alkyl, alkenyl, alkynyl group, carbocylic radical and the heterocyclic radical that replace can comprise one or more polymkeric substance.These substituting groups for example, comprise fluorine, chlorine, D etc.In addition, heterocyclic radical can comprise O, N, S etc.
Aryl preferably includes, but is not limited to benzyl, phenyl, fluorenyl and naphthyl.These aryl, carbocylic radical, heterocyclic radical and cyclohexyl also can be replaced by one or more substituting groups.These substituting groups for example, comprise D, halogen, as fluorine, chlorine and bromine.Alkylaryl preferably includes C 1-C 10Alkyl, the alkylaryl of replacement comprise the above-mentioned alkyl and the substituting group of aryl.
In the preferred embodiment of the present invention, R 2And R 3Be selected from the phenyl of benzyl, carbocylic radical, heterocyclic radical, cyclohexyl, phenyl, cycloalkyl, cycloalkenyl group and replacement separately respectively.R 2And/or R 3Other groups include, but are not limited to following group respectively: Deng.
In the embodiment that the present invention is more preferably, R 2And R 3In one be CH 3, another is the phenyl that replaces.This substituted-phenyl is preferably selected from as next group, but is not limited thereto:
Figure A0180835600172
Deng.
Perhaps, R 2And R 3Form ring structure or substituted ring structure together.Above-mentioned ring structure contains 3-7 atom altogether, better contains 5-6 atom.Above-mentioned ring structure preferably replaces or unsubstituted carbocyclic ring, replaces or unsubstituted heterocycle, replaces or unsubstituted cyclohexyl or cyclopentyl.The ring structure of above-mentioned replacement can contain substituting group.This substituting group includes, but are not limited to halogen, as fluorine, chlorine and bromine.
Have by R 2And R 3The preferred compound of the ring structure that forms comprises:
Electron-withdrawing group of the present invention is preferably pressed reaction scheme I preparation:
Figure A0180835600181
Reaction circuit I
The compound of representing with general formula I preferably prepares by the following steps shown in the reaction scheme I: a) provide alkyl vinyl ether; B) described alkyl vinyl ether is contacted with highly basic, form first intermediate compound; C) described first intermediate compound is contacted with ketone, form second intermediate compound; D) in the presence of second kind of alkali, make described second intermediate compound and dicyano methane reaction, form the electron-withdrawing group of compound of Formula I.Below above-mentioned described each step is described in more detail.
In the preferred embodiment of the present invention, alkyl vinyl ether is a raw material in the solvent.The preferred tetrahydrofuran (THF) of above-mentioned solvent (THF), 1,4-diox etc.Though the alkyl vinyl ether shown in the reaction scheme I is an ethyl vinyl ether, also can use other alkyl vinyl ethers.The more handy general formula CH of this alkyl vinyl ether 3(CH 2) x-O-CH=CHR 6, x is 1-3 in the formula, R 6Be C 1-C 4Alkyl.Alkyl vinyl ether is methylvinylether or ethyl vinyl ether preferably.
Alkyl vinyl ether contacts with highly basic, forms first intermediate compound.Alkaline pKa is greater than ethylenic (ethylinic) c h bond on the described alkyl vinyl ether oxygen functional group alpha position.For example referring to " senior organic chemistry " third edition, Jerry March, 1985, table 1,220-222 page or leaf.In a preferred embodiment of the invention, highly basic is lithium alkylide, or the anionic an alkali metal salt of alkyl, comprises tert-butyl lithium or s-butyl lithium.Alkyl vinyl ether is more fortunately-70 ℃ between-85 ℃ the temperature, better approximately-78 ℃ contact with highly basic.
First intermediate compound contacts with ketone, contacts with acid/alcohol/aqueous solution then, forms second intermediate compound.The known many acid/alcohol of those skilled in the art/aqueous solution can be used among the present invention.This acid/alcohol/aqueous solution better is HCl/MeOH/H 2O, HBr/EtOH/H 2O or H 2SO 4/ EtOH/H 2O.Contact is better at room temperature carried out.PH better is adjusted between the 1-4.
Above-mentioned ketone better comprises R 3-C (=O) R 2, R separately in the formula 2And R 3Be selected from and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.
" C 1-C 10" be meant C 1, C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10And the combination of these scopes.
The C=C of alkenyl and alkynyl group and C ≡ C key better not with the tight adjacent or conjugation of the carbonyl of ketone compound.
The alkyl, alkenyl, alkynyl group, carbocylic radical and the heterocyclic radical that replace can contain one or more substituting groups, for example comprise fluorine, chlorine, D etc.In addition, heterocyclic radical can comprise O, N, S etc.
Aryl better includes, but are not limited to benzyl, phenyl, fluorenyl and naphthyl.Aryl, carbocyclic ring, heterocycle and cyclohexyl also can be replaced by one or more substituting groups.These substituting groups for example comprise D, halogen.Above-mentioned halogen comprises fluorine, chlorine and bromine.Alkylaryl better comprises C 1-C 10Alkyl, and the alkylaryl that replaces comprises the substituent of abovementioned alkyl and aryl.
In the preferred embodiment of the present invention, R 2And R 3Be selected from the phenyl of benzyl, carbocyclic ring, heterocycle, cyclohexyl, phenyl, cycloalkyl, cycloalkenyl group and replacement separately respectively.R 2And/or R 3Other groups include, but are not limited to following group respectively: Deng.
In the embodiment that the present invention is more preferably, R 2And R 3In one be CH 3, and R 2And R 3In another is the phenyl that replaces.The phenyl that replaces better is selected from as next group, but is not limited to this: Deng.
Perhaps, R 2And R 3Form ring structure or substituted ring structure together.Above-mentioned ring structure contains 3-7 atom altogether, better contains 5-6 atom.Above-mentioned ring structure preferably replaces or unsubstituted carbocyclic ring, replaces or unsubstituted heterocycle, replaces or unsubstituted cyclohexyl or cyclopentyl.The ring structure of above-mentioned replacement can contain substituting group.This substituting group includes, but are not limited to halogen, as fluorine, chlorine and bromine.Have by R 2And R 3The preferred compound of the ring structure that forms comprises:
Second intermediate compound in the presence of second kind of alkali with the dicyano methane reaction, form the electron-withdrawing group part of compound shown in the general formula I.Second kind of alkali better is metal alkoxide, and it includes but not limited to NaOC 2H 5After making second intermediate compound and dicyano methane contacts under the condition that second kind of alkali exists, add diluted acid, as HCl, with the electron-withdrawing group of neutralization generation.
Electron-withdrawing group comprises R 6It better is selected from the replacement of non-collateralization or does not replace C 1-C 4Alkyl, not collateralization replacement or do not replace C 2-C 4Alkenyl, the not replacement or the unsubstituted C of collateralization 2-C 4Alkynyl group.The alkyl, alkenyl and the alkynyl group that replace can comprise one or more substituting groups, as comprise fluorine.In preferred implementation of the present invention, R 6Be selected from the not C of collateralization 1-C 4Alkyl, C 1-C 4Alkenyl and C 1-C 4Alkynyl group.In the preferred embodiment of the present invention, R 6Be CH 3
The present invention also part relates to the compound that can be used as chromophore compound in the optical waveguides polymeric film.This compound comprises the novel abutment of this chromophoric group electron-withdrawing group of energy coupling and electron-donating group.Preferred compound of the present invention is represented with general formula I I:
Figure A0180835600202
D is an electron-donating group.Preferred electron-donating group as mentioned above.
A is an electron-withdrawing group.Preferred electron-withdrawing group for example is documented in United States Patent (USP) 5,044,725,4,795,664,5,247,042,5,196,509,4,810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.Every patent is all with reference to being incorporated among the application.A better is selected from the molecular cell including (but not limited to) following one group of group: nitro, cyano group, haloalkyl, acyl group, carboxyl, aryloxy, amide group, alkoxyl group alkylsulfonyl, aryloxy sulfonyl ,-CH=C (CN) 2,-C (CN)=C (CN) 2, SO 2CF 3, alkanoyloxy,
Figure A0180835600211
With
Figure A0180835600212
X is H, D, F, CN, NO in the formula 2Or CF 3
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q better do not exist, but when existing, is O or S; Q is 1,2 or 3.R 1Be more preferably C 1-C 10Or the C of fluorine replacement 4-C 10
The compound of representing with general formula I I can prepare with the thiophene ring-type bridge that more handy general formula VII represents:
K is preferably O or S.
R 1Better be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q better do not exist, but when existing, is O or S.Also available other halogens or deuterium replace fluorine.In the preferred embodiment of the present invention, R 1Be more preferably C 4-C 10Or the C of fluorine replacement 4-C 10
The b-C of the more handy general formula of X-(CH=CH) (=O) H represents, b is 0-3 in the formula.Terminal aldehyde radical is used as the preferred site with the electron-withdrawing group reaction.In more preferably embodiment of the present invention, b is 0, and X is-C (=O) H like this.
Z be can with the chemical group that is connected to body, it include, but is not limited to Br, I ,-CH 2Br-,-CH 2OH ,-CH 3,-C (=O) H etc.Those skilled in the art can use as known in the art bridge shape compound can being connected to other groups on the body.Another kind can be used for bridge shape compound is connected to the Z group on the body
Figure A0180835600214
Y in the formula -Be gegenion, it includes but not limited to Br -Or Cl -
In other embodiments of the present invention, preferred compound of the present invention is represented with general formula III:
D is an electron-donating group, and A is above-mentioned electron-withdrawing group.J is CH 2, O or S.
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q do not exist, or is O or S.R 1Be more preferably C 4-C 10Or the C of fluorine replacement 4-C 10
Compound shown in the general formula I V can prepare with the difluoro naphthyl ring-type bridge construction that more handy general formula VIII represents:
J better is CH 2, O or S.
R 1Better be H ,-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q do not exist, or is O or S.Also available other halogens or deuterium replace fluorine.In the preferred embodiment of the present invention, R 1Be more preferably C 4-C 10Or the C of fluorine replacement 4-C 10
The more handy general formula of X (C=O) H or C=CH are (CH=CH) d-C (=O) H represents, d is 0-3 in the formula.Terminal aldehyde radical or ketone group are used as the preferred site with the electron-withdrawing group reaction.In more preferably embodiment of the present invention, X is-C (=O) H.
Z is the above-mentioned chemical group that can be connected to on the body.
The present invention also part relates to the compound that can be used as chromophore compound in the optical waveguides polymeric film.This compound comprises novel abutment and novel electron-withdrawing group, and represents with general formula I V: K is O or S in the formula; With
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q do not exist, or is O or S; Q is 1,2 or 3.In the more preferably embodiment of the present invention, R 1Be C 4-C 10Or the C of fluorine replacement 4-C 10Preferred compound general formula I V ' expression in the above-mentioned embodiment of this present invention: In the formula:
R 2And R 3Further characteristics are ring structures that they determine a ring structure or replacement, and wherein * represents spiro junction or expression chiral centre.
Perhaps, R 2And R 3Be selected from respectively separately, but be not limited to replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10 etc.R 2And R 3Be selected from better respectively and replace or unsubstituted aryl, replacement or unsubstituted alkyl aryl and replacement or unsubstituted cyclohexyl.R 2And R 3Be selected from benzyl, cyclohexyl and replacement respectively or unsubstituted phenyl is better.More preferably, R 2And R 3In one be CH 3, R 2And R 3In another be the phenyl that replaces.Most preferably, R 2And R 3In one be: And R 2And R 3In another be CH 3
Perhaps, R 2And R 3Form ring structure or substituted ring structure together.Above-mentioned ring structure contains 3-7 atom altogether, better contains 5-6 atom.Above-mentioned ring structure preferably replaces or unsubstituted carbocyclic ring, replaces or unsubstituted heterocycle, replaces or unsubstituted cyclohexyl or cyclopentyl.The ring structure of above-mentioned replacement can contain substituting group.This substituting group includes, but are not limited to deuterium and halogen.Halogen comprises fluorine, chlorine and bromine.Have by R 2And R 3The preferred compound of the ring structure that forms comprises:
D is above-mentioned electron-donating group.
In other preferred implementations of the present invention, useful compound is represented with the structure of general formula V: J is CH in the formula 2, O or S.
R 1Better be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S.In more preferably embodiment of the present invention, R 1Be C 4-C 10Or the C of fluorine replacement 4-C 10Preferred compound general formula V in the above-mentioned embodiment of the present invention 1Expression:,
Figure A0180835600243
In the formula:
R 2And R 3The characteristics of advancing-going on foot are ring structures that they determine a ring structure or replacement, and wherein * represents spiro junction or expression chiral centre.
Perhaps, R 2And R 3Be selected from respectively separately, but be not limited to replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10, or the like.R 2And R 3Be selected from better respectively and replace or unsubstituted aryl, replacement or unsubstituted alkyl aryl and replacement or unsubstituted cyclohexyl.R 2And R 3Be selected from benzyl, cyclohexyl and replacement respectively or unsubstituted phenyl is better.More preferably, R 2And R 3In one be CH 3, R 2And R 3In another be the phenyl that replaces.Most preferably, R 2And R 3In one be: And R 2And R 3In another be CH 3
Perhaps, R 2And R 3Form ring structure or substituted ring structure together.Above-mentioned ring structure contains 3-7 atom altogether, better contains 5-6 atom.Above-mentioned ring structure preferably replaces or unsubstituted carbocyclic ring, replaces or unsubstituted heterocycle, replaces or unsubstituted cyclohexyl.The ring structure of above-mentioned replacement can contain substituting group.This substituting group includes, but are not limited to deuterium and halogen.Halogen comprises fluorine, chlorine and bromine.Have by R 2And R 3The preferred compound of the ring structure that forms comprises:
Figure A0180835600252
D is above-mentioned electron-donating group.
The present invention also part relates to the optical waveguides that contains polymeric film.Above-mentioned polymeric film contains chromophore compound of the present invention.In preferred implementation of the present invention, the contained thin film dielectrics of optical waveguides is represented with general formula VI: Or
Figure A0180835600262
P and P ' are the main polymer chain unit, can be identical monomeric unit or different monomeric units, and C is a comonomer unit; N is the integer greater than 0; N ' is 0 or greater than 0 integer.Can be used for polymkeric substance of the present invention and multipolymer and for example be documented in United States Patent (USP) 5,044,725,4,795,664,5,247,042,5,196,509,4,810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.Every patent is all with reference to being incorporated among the application.Polymkeric substance of the present invention can be homopolymer or multipolymer.Preferred polymkeric substance and multipolymer include, but are not limited to polyacrylic ester, poly carboxylic acid vinyl acetate, the poly-aryl ethylene that replaces, polyvinylhalide, poly carboxylic acid vinyl acetate, polyolefine, polyalkadiene, poly-aryl ethylene, polymethacrylate, polyvinyl chloride, polyvinyl acetate, polyvinyl ether, polyethylene, polypropylene, polyisobutene, poly-1-butylene, polyisoprene, polystyrene etc.
Polymkeric substance of the present invention better contains the side chain of induced orientation and arrangement outside the venue.Main polymer chain better can be following structure type: polyethylene, polyoxyalkylene, polysiloxane, polycondensation etc.Polymkeric substance can be coated to the mode of routine on the supporting substrate: spin-coating method, dip coating, spraying method, Langmuir-Blodgett sedimentation etc.After making, thin film optical wave-guide of the present invention can be subjected to the effect in outfield, so that polymer lateral chain uniaxial orientation and arrangement.In one approach, with polymeric media be heated near or surpass the glass transition temperature Tg of this polymkeric substance, medium to removable chromophore compound molecule applies an outfield (as DC electric field) then, induce color development polymer lateral chain single shaft to molecular arrangement or the field that object in host and guest's system is parallel to apply, keeping under the outer field action above-mentioned medium cooling then.
S is separation (spacer) side group that straight chain length is about 2-12 atom.Can be used for separation side group of the present invention, for example be documented in United States Patent (USP) 5,044,725,4,795,664,5,247,042,5,196,509,4,810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.Every patent is all with reference to being incorporated among the application.
M is above-mentioned with general formula I, general formula I ', the chromophore compound of general formula I I, general formula III, general formula I V, general formula I V ', general formula V or general formula V ' expression.
The present invention also part relates to the optics that contains optical waveguides of the present invention.Optics for example is documented in United States Patent (USP) 5,044, and 725,4,795,664,5,247,042,5,196,509,4,810,338,4,936,645,4,767,169,5,326,661,5,187,234,5,170,461,5,133,037,5,106,211 and 5,006,285.Every patent is all with reference to being incorporated among the application.Preferred optics includes, but are not limited to United States Patent (USP) 4,775, the laser frequency transmodulator described in 215, optical interdferometer waveguide grid, broadband photoelectricity guided wave analog(ue)digital transformer and optical reference device.Above-mentioned patent reference is incorporated among the application.
The present invention is further described by following embodiment.These embodiment are used to explain the present invention.These embodiment also are not used in, and can not be interpreted as the restriction to open scope.
Embodiment
Embodiment 1: the general synthetic method of dicyano methylene radical dihydrofuran
Be dissolved in the solution of 150 milliliters of dry THF to 0.33 mole of ethyl vinyl ether, at-78 ℃ of pentane solutions that drip 0.3 mole of tert-butyl lithium.Stir this mixture, and allow it slowly be warming up to 0 ℃, and then be cooled to-78 ℃.Then, drip 0.25 mole of cyclohexyl phenyl ethereal solution that is dissolved in the minimum dry tetrahydrofuran.Under the room temperature this mixture stirring is spent the night, use HCl/MeOH/THF/H then 2It is 1-4 that O solution is acidified to pH.This mixture stirring after two hours, is evaporated most of solvent with Rotary Evaporators.Remaining mixture is with 100 milliliters of extracted with diethyl ether 3 times.Organic solution NaHCO 3, salt solution and deionized water wash.Use anhydrous MgSO then 4Dried overnight.Evaporate after the ether, crude product is purified with column chromatography (containing 5% ethyl acetate in the hexane), produces pure alpha-alcohol ketone (30 gram).
Under the ice bath cooling, the ethanolic soln (by propane dinitrile, 20% w/v) of above-mentioned synthetic hydroxyketone (0.02 mole) with propane dinitrile (0.04 mole) mixed.In this mixture, drip 20 milliliters of 1MNaOC 2H 5/ EtOH.Allowing this mixture stir spends the night.After being neutralized to pH6 with concentrated hydrochloric acid, solvent is fallen in vacuum distilling.Resistates is dissolved in the methylene dichloride, removes by filter undissolved solid.After distilling methylene dichloride,, obtain dicyano methylene radical dihydrofuran compound (1.25 gram) with the ethyl alcohol recrystallization crude product of purifying.
Perhaps, and be more preferably, above-mentioned synthetic hydroxyketone (0.02 mole) is mixed with propane dinitrile (0.04 mole) that is dissolved in THF (40 milliliters) and EtOH (2 milliliters) and salt of wormwood (0.02 mole).In this mixture, add the hexaoxacyclooctadecane-6 of catalytic amount.Allow this mixture stirring and refluxing spend the night.Solid filtering is fallen, distill most of solvent then.Crude product column chromatography (CH 2Cl 2) purify, obtain dicyano methylene radical dihydrofuran compound as follows (1.5 gram) (fusing point MP=194-196 ℃).
Figure A0180835600281
Embodiment 2: based on the preparation method of the electron acceptor(EA) of dicyano methylene radical dihydrofuran
In the time of-78 ℃, be added dropwise to 176 milliliters of tert-butyl lithium to ethyl vinyl ethereal solution (28.8 grams are dissolved among 300 milliliters of THF).This mixture slowly is warmed to 0 ℃, and then is cooled to-78 ℃.Drip pimelinketone (30 grams are dissolved among 30 milliliters of THF), allow this mixture slowly be warming up to room temperature, restir 4 hours.In this reaction mixture, slowly add the solution of methyl alcohol (70 milliliters), water (20 milliliters) and concentrated hydrochloric acid (10 milliliters), reach about 2-3 up to pH.Allow mixture stir and spend the night, add 20%NaHCO 3The aqueous solution is neutralized to pH7 with it, distills solvent then.Remaining solvent is with 100 milliliters of extracted with diethyl ether 3 times.Ethereal solution NaHCO 3The washing of (50 milliliters), salt solution (100 milliliters).Use anhydrous MgSO then 4Dried overnight.Evaporate after the ether, this intermediate product of vacuum distilling obtains 36 grams.
In ice bath, with CH 2(CN) 2(13.2 gram) and 1M NaOC 2H 5(0.1 mole) solution mixes.Be added dropwise to about 14.2 and restrain the above-mentioned minimum alcoholic acid intermediate that makes and be dissolved in, at room temperature stir then and spend the night.With 8 milliliters of concentrated hydrochloric acids said mixture is neutralized to pH6.0, after filtering solid matter, and distills all the other solution.The resistates that produces in this solution is dissolved in the methylene dichloride, filters once more, distill methylene dichloride then.Remaining mixture obtains 6.1 grams target compound (mMP=239-241 ℃) as follows with ethanol (150 milliliters) recrystallization.
Embodiment 3: based on the preparation method of the electron acceptor(EA) of dicyano methylene radical dihydrofuran
In the time of-78 ℃, be added dropwise to 110 milliliters of tert-butyl lithium to ethyl vinyl ethereal solution (21.6 grams are dissolved among 300 milliliters of THF).This mixture slowly is warmed to 0 ℃, and then is cooled to-78 ℃.5 ', 4 '-dichloroacetophenone (30.5 gram) is dissolved in 150 milliliters of tetrahydrofuran (THF)s, drips then.Under the room temperature this mixture stirring is spent the night.The solution that in this reaction mixture, slowly added methyl alcohol (70 milliliters), water (20 milliliters) and concentrated hydrochloric acid (10 milliliters) in second day.With mixture pH regulator to 4, stirring is spent the night.Add NaHCO 3The aqueous solution is neutralized to pH7 with it.Mixture is with 100 milliliters of extracted with diethyl ether 3 times.The organic acid soln NaHCO that merges 3Anhydrous MgSO is used in the washing of (50 milliliters), salt solution (100 milliliters) then 4Dried overnight.This intermediate product of vacuum distilling obtains 55 grams.
In ice bath, with CH 2(CN) 2(13.2 gram) and 1M NaOC 2H 5(0.1 mole) solution mixes.Be added dropwise to the above-mentioned intermediate that makes and be dissolved in the ethanol of about 15 grams, at room temperature stir then and spend the night.With 8 milliliters of concentrated hydrochloric acids said mixture is neutralized to pH6.0, after filtering solid matter, and distillation gained solution.Resistates is dissolved in the methylene dichloride, filters once more, distill methylene dichloride then.Remaining mixture obtains 5.5 grams target compound as follows (fusing point from left to right equals 110-111 ℃ respectively, 152-153 ℃ and 222-224 ℃) with ethanol (150 milliliters) recrystallization.
Figure A0180835600291
Embodiment 4: the preparation method of trans-[(N, N-two (2-ethanol) amino) phenylene-3-decyl-2-thiophene]
At bromination 3-decyl-2-methyl three fourth base Phosphonium-thiophene (26 grams, 0.05 mole) and N, N-diethanolamine benzaldehyde (12.6 grams, 0.06 mole) is dissolved in 200 milliliters of alcoholic acid solution, is added dropwise to NaOC 2H 5(1M ethanolic soln).The mixture that forms was refluxed 98 hours.Take out reaction mixture from oil bath after, distill solvent, resistates is with 150 milliliters of extracted with diethyl ether 3 times.The ether mixture that merges with the washing of 100 ml waters once with 100 milliliters of washings 2 times, is used anhydrous magnesium sulfate drying then.After distilling solvent, resistates is purified with silica gel column chromatography, with 50% ethyl acetate, 10% acetone and 40% hexane wash-out, obtains pure target compound, and output is 16 grams.Carbon and proton N MR are consistent with structure.
Embodiment 5
The preparation method of trans-[(N, N-two (2-ethanol) amino) phenylene-2-thiophene 3-last of the ten Heavenly stems the-5-aldehyde]
In 500 ml flasks that above-mentioned synthetic compound (10.44 grams, 0.0243 mole) is housed, add 200 milliliters of THF.This solution is cooled to-78 ℃, drips n-Butyl Lithium (32 milliliters, the 2.5M hexane solution) then.Reaction mixture was stirred 2 hours, add DMF (6 milliliters) then.Under the room temperature solution stirring that forms is spent the night.After adding HCl (2M, 50 milliliters) and stirring 1 hour, distill THF.Resistates extracted with diethyl ether 3 times are used 100 milliliters at every turn.The saturated Na of organic solution that merges 2CO 3Anhydrous magnesium sulfate drying is used in solution (50 milliliters), water (100 milliliters), salt solution (100 milliliters) washing then.After the solvent evaporated, obtain solid target compound (11.1 grams, fusing point is 107-109 ℃).HNMR shows that this compound is quite pure, can be directly used in next step.
Embodiment 6
The preparation chromophore compound
With above-mentioned aldehyde cpd (3 grams, 6.54 mmoles) and 2-dicyano methylene radical-3-cyano group-4,5-dimethyl-5-(3, the 4-dichlorophenyl)-2,5-dihydrofuran (2.4 grams, 7.27 mmoles) mixes and is dissolved in the ethanol (30 milliliters).Add 2 or 3 piperidines.This mixture was refluxed 48 hours.After the cooling, the solid of filtering-depositing is used ethyl alcohol recrystallization, purifies with the chromatography silica gel eluting solvent, obtains 3.38 gram chromophore compounds.The analytical results of carbon and proton N MR conforms to its structure.
Embodiment 7: the preparation chromophore compound
In ethanol (20 milliliters), incite somebody to action anti--[(N, N-two (2-ethanol) amino) phenylene-3,4-dibutyl-2-thiophene-5-aldehyde] (0.3 gram, 0.7 mmole) with 2-dicyano methylene radical-3-cyano group-4,5-dimethyl-5-(3, the 4-dichlorophenyl)-2,5-dihydrofuran (0.23 gram, 0.7 mmole) mixes.Add 2 or 3 piperidines.This mixture was refluxed 48 hours.After the cooling, the solid of filtering-depositing is used ethyl alcohol recrystallization, purifies with the chromatography silica gel eluting solvent.
Embodiment 8: the preparation of high chlorination electro-optic polymer
Be equipped with 1 at one, 4,5,6,7,7-chlordene-5-norbornylene-2,3-dicarboxyl acyl chlorides (2.65 grams, 6.23 mmole) and 2,3,5,6-tetrachloro-p-Xylol-α, in the three-necked flask of salmefamol (1.36 gram, 4.93 mmoles), in 70 ℃ and 20 milliliters of THF, be mixed into 2-dicyano methylene radical-3-cyano group-4-{2-[E-N, N-two (2-ethanol) amino) phenylene-(3-decyl) thiophene-5]-the E-vinyl }-5-methyl-5-(3, the 4-dichlorophenyl)-2,5-dihydrofuran (1 gram, 1.3 mmoles).Drip Et 3N (1.26 grams are dissolved in 15 milliliters of THF).Under argon atmospher, this mixture was refluxed 48 hours.After distilling some THF, under vigorous stirring, remaining solution is slowly splashed in MeOH (300 milliliters) and the water (50 milliliters).The solid of filtering-depositing is dissolved in it among THF again, once more precipitation in methyl alcohol (300 milliliters).With the solid vacuum-drying of collecting 8 hours, claim to such an extent that weight is 4.5 grams.Characterize this polymkeric substance with DSC and TGA.Tg is 152 ℃, and airborne decomposition temperature is 285 ℃.
Though for the purpose of explaining, the present invention has been done detailed description, but be to be understood that these details only are used for this purpose, various changes can be made under the condition that does not depart from the spirit and scope of the invention that is limited by following claims for those skilled in the art.

Claims (39)

1. the compound represented of general formula I I:
Figure A0180835600021
In the formula:
K is O or S;
D is an electron-donating group;
A is an electron-accepting group;
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S; Q is 1,2 or 3.
2. the compound of representing with general formula III In the formula:
J is CH 2, O or S;
D is an electron-donating group;
A is an electron-accepting group;
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S.
3. compound as claimed in claim 1 or 2 is characterized in that A is selected from following one group molecular cell: nitro, cyano group, haloalkyl, acyl group, carboxyl, aryloxy, amide group, alkoxyl group alkylsulfonyl, aryloxy sulfonyl ,-CH=C (CN) 2,-C (CN)=C (CN) 2, SO 2CF 3, alkanoyloxy,
Figure A0180835600023
With X is H, D, F, CN, NO in the formula 2Or CF 3
4. compound as claimed in claim 3 is characterized in that a is 1-3, and n is 1-3.
5. compound as claimed in claim 4 is characterized in that R 1Be C 4-C 10Or the C of fluorine replacement 4-C 10
6. use general formula I ' expression compound:
Figure A0180835600031
In the formula:
R 2And R 3Determine the ring structure of ring structure or replacement, wherein * represents spiro junction or expression chiral centre; Or R 2And R 3Respectively do for oneself and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10; Prerequisite is to work as R 2And R 3All be selected from and replace or unsubstituted C 1-C 10During alkyl, R 2≠ R 3
D is an electron-donating group; With
B comprises at least one divalence aromatic ring.
7. compound as claimed in claim 6 is characterized in that B is selected from: R in the formula 4Be H, OH, C 1-C 10Alkyl, alkenyl, alkynyl group or halogen.
8. compound as claimed in claim 7 is characterized in that R 2And R 3Be selected from separately and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10; Prerequisite is to work as R 2And R 3All be selected from and replace or unsubstituted C 1-C 10During alkyl, R 2≠ R 3
9. compound as claimed in claim 8 is characterized in that R 2And R 3Be selected from separately and replace or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic and replacement or unsubstituted cyclohexyl.
10. use the compound of general formula I V ' expression:
Figure A0180835600042
In the formula:
R 2And R 3The ring structure of stop collar structure or replacement, wherein * represents spiro junction or expression chiral centre; Or R 2And R 3Respectively do for oneself and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10;
D is an electron-donating group;
K is O or S;
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is 0-10, and Q vacancy or be O or S;
Q is 1,2 or 3.
11. compound as claimed in claim 10 is characterized in that R 2And R 3Be selected from separately and replace or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic and replacement or unsubstituted cyclohexyl.
12. use the compound of general formula V ' expression
Figure A0180835600051
In the formula:
R 2And R 3The ring structure of stop collar structure or replacement, wherein * represents spiro junction or expression chiral centre; Or R 2And R 3Respectively do for oneself and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10;
D is an electron-donating group;
J is CH 2, or S;
R 1Be-Q-C nH 2n+1,-Q-(CH 2) aC nF 2n+1,-Q-CH 2OCH 2C nF 2n+1,-Q-CH 2SCH 2CC nF 2n+1,-Q-CH 2OCH 2CF 3Or-Q-CH 2SCH 2CF 3, wherein n is 1-10, a is O-10, and Q vacancy or be O or S;
13. compound as claimed in claim 12 is characterized in that R 2And R 3Be selected from separately and replace or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic and replacement or unsubstituted cyclohexyl.
14. as each described compound in the claim 1,2,6,10 or 12, it is characterized in that D is that contraposition is selected from the phenyl ring that following one group group replaces: amino, alkylamino, dialkyl amido, dialkyl benzene amino, piperidino, 1-piperazinyl, 1-pyrrolidyl, amido, hydroxyl, thiol group, alkylthio, arylthio, alkoxyl group, aryloxy, acyloxy, alkyl, vinyl and 1,2,3, the 4-tetrahydric quinoline group.
15., it is characterized in that R as each described compound in the claim 6,10 or 12 2And R 3Be selected from benzyl, cyclohexyl, cyclopentyl and replacement or unsubstituted phenyl separately.
16., it is characterized in that R as each described compound in the claim 6,10 or 12 2And R 3In one be CH 3, R 2And R 3In another is a substituted-phenyl.
17. compound as claimed in claim 16 is characterized in that described substituted-phenyl is
18., it is characterized in that R as each described compound in the claim 6,10 or 12 2And R 3Be different, and all be selected from replacement or unsubstituted C 1-C 10Alkyl.
19., it is characterized in that R as each described compound in the claim 6,10 or 12 2And R 3Form the ring structure of ring structure or replacement together.
20. compound as claimed in claim 19 is characterized in that R 2And R 3Form cyclohexyl or cyclopentyl together.
21., it is characterized in that R as claim 10 or 12 described compounds 2And R 3Be selected from separately and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.
22., it is characterized in that a is 1-3, and n is 1-3 as claim 10 or 12 described compounds.
23., it is characterized in that R as claim 10 or 12 described compounds 1Be C 4-C 10Or the C of fluorine replacement 4-C 10
24. an optical waveguides is characterized in that it comprises the thin film dielectrics of representing with general formula VI: Or
Figure A0180835600072
In the formula:
P and P ' are the main polymer chain unit;
C is a comonomer unit;
S is the separation side group that straight chain length is about the 2-12 atom;
N is the integer greater than 0;
N ' is 0 or greater than 0 integer;
M is each described compound among the claim 1-23.
25. an optics is characterized in that it contains the optical waveguides described in the claim 24.
26. optics as claimed in claim 25 is characterized in that described device is selected from laser frequency transmodulator, optical interdferometer waveguide grid, broadband photoelectricity guided wave analog(ue)digital transformer and optical reference device.
27. the preparation method of an electron-withdrawing group is characterized in that it comprises the steps:
(a) provide alkyl vinyl ether;
(b) described alkyl vinyl ether is contacted with highly basic, form first intermediate compound;
(c) described first intermediate compound is contacted with ketone, form second intermediate compound;
(d) in the presence of second kind of alkali, make described second intermediate compound and dicyano methane reaction, form described electron-withdrawing group.
28. method as claimed in claim 27 is characterized in that described alkyl vinyl ether is in solvent.
29. method as claimed in claim 28 is characterized in that described solvent is tetrahydrofuran (THF) or 1, the 4-diox.
30. method as claimed in claim 29, the general formula that it is characterized in that described alkyl vinyl ether is CH 3(CH 2) x-O-CH=CHR 6, x is 1-3 in the formula, R 6Be H or C 1-C 4Alkyl.
31. method as claimed in claim 29 is characterized in that described alkyl vinyl ether is methylvinylether or ethyl vinyl ether.
32. method as claimed in claim 27 is characterized in that described alkaline pKa is greater than ethylenic c h bond on the described alkyl vinyl ether oxygen functional group alpha position.
33. method as claimed in claim 32 is characterized in that described highly basic is lithium alkylide.
34. method as claimed in claim 33 is characterized in that described lithium alkylide is tert-butyl lithium or s-butyl lithium.
35. method as claimed in claim 27, the general formula that it is characterized in that described ketone is R 3-C (=O) R 2, R in the formula 2And R 3Be selected from separately and replace or unsubstituted C 1-C 10Alkyl, replacement or unsubstituted C 2-C 10Alkenyl, replacement or unsubstituted C 2-C 10Alkynyl group, replacement or unsubstituted aryl, replacement or unsubstituted alkyl aryl, replacement or unsubstituted carbocylic radical, replacement or unsubstituted heterocyclic, replacement or unsubstituted cyclohexyl or (CH 2) n-O-(CH 2) n, wherein n is 1-10.
36. method as claimed in claim 35 is characterized in that R 2And R 3Be selected from benzyl, cyclohexyl, cyclopentyl, phenyl and substituted-phenyl separately.
37. method as claimed in claim 36 is characterized in that described R 2And R 3In one be CH 3, another is a substituted-phenyl.
38. method as claimed in claim 27 is characterized in that described second kind of alkali is metal alkoxide.
39. method as claimed in claim 38 is characterized in that described metal alkoxide is NaOC 2H 5
CN 01808356 2000-06-16 2001-05-16 Novel chromophores for polymeric thin films and optical waveguide and devices comprising the same Pending CN1425018A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/595,221 US6584266B1 (en) 2000-06-16 2000-06-16 Chromophores for polymeric thin films and optical waveguides and devices comprising the same
US09/595,221 2000-06-16
US09/675,966 2000-09-29
US09/675,966 US6393190B1 (en) 2000-06-16 2000-09-29 Chromophores for polymeric thin films and optical waveguides and devices comprising the same

Publications (1)

Publication Number Publication Date
CN1425018A true CN1425018A (en) 2003-06-18

Family

ID=27082199

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 01808356 Pending CN1425018A (en) 2000-06-16 2001-05-16 Novel chromophores for polymeric thin films and optical waveguide and devices comprising the same

Country Status (6)

Country Link
EP (1) EP1290000A4 (en)
JP (1) JP2004501159A (en)
CN (1) CN1425018A (en)
AU (1) AU2001263187A1 (en)
CA (1) CA2411963A1 (en)
WO (1) WO2001098310A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482504A (en) * 2009-08-24 2012-05-30 独立行政法人情报通信研究机构 Second-order non-linear optical compound and non-linear optical element comprising same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7723462B2 (en) 2006-05-03 2010-05-25 Corning Incorporated Mercaptofunctional high mubeta EO chromophores and high Tg, low optical loss, covalently bonded, high mubeta EO chromophore containing polymers and methods of synthesizing EO materials
JP5376359B2 (en) * 2008-09-08 2013-12-25 住友電気工業株式会社 Nonlinear optical compound, nonlinear optical material, and nonlinear optical element
EP3674792A4 (en) 2017-08-24 2021-04-14 National Institute of Information and Communications Technology Laminate for non-linear optics containing electro-optic polymer layer and method for producing same
US20210032228A1 (en) * 2018-01-30 2021-02-04 National Institute Of Information And Communications Technology Electro-optic polymer
JP2023124449A (en) 2022-02-25 2023-09-06 国立研究開発法人情報通信研究機構 Electro-optical polymer element

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5044725A (en) * 1986-01-24 1991-09-03 Hoechst Celanese Corp. Polymeric thin film waveguide media
GB9019347D0 (en) * 1990-09-05 1990-10-17 Ici Plc Chromophore-containing compounds for opto-electronic applications
US5882785A (en) * 1997-01-23 1999-03-16 The United States Of America As Represented By The Secretary Of The Navy Nonlinear optical films from pair-wise-deposited semi-ionomeric syndioregic polymers
US6361717B1 (en) * 1998-07-27 2002-03-26 Pacific Wave Industries, Inc. Sterically stabilized second-order nonlinear optical chromophores and devices incorporating the same
US6348992B1 (en) * 1998-07-27 2002-02-19 Pacific Wave Industries, Inc. Sterically stabilized polyene-bridged second-order nonlinear optical chromophores and devices incorporating the same
US6067186A (en) * 1998-07-27 2000-05-23 Pacific Wave Industries, Inc. Class of high hyperpolarizability organic chromophores and process for synthesizing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482504A (en) * 2009-08-24 2012-05-30 独立行政法人情报通信研究机构 Second-order non-linear optical compound and non-linear optical element comprising same
CN104610774A (en) * 2009-08-24 2015-05-13 独立行政法人情报通信研究机构 Second-order nonlinear optical compound and nonlinear optical element comprising the same
CN102482504B (en) * 2009-08-24 2016-01-20 独立行政法人情报通信研究机构 Second nonlinear optic compound and containing its nonlinear optical element
CN104610774B (en) * 2009-08-24 2017-07-18 独立行政法人情报通信研究机构 Second nonlinear optic compound and the nonlinear optical element containing it

Also Published As

Publication number Publication date
JP2004501159A (en) 2004-01-15
EP1290000A4 (en) 2005-07-20
EP1290000A1 (en) 2003-03-12
WO2001098310A1 (en) 2001-12-27
AU2001263187A1 (en) 2002-01-02
CA2411963A1 (en) 2001-12-27

Similar Documents

Publication Publication Date Title
EP1313729B1 (en) Design and synthesis of thiophene derived nlo materials for electro-optic applications
US6393190B1 (en) Chromophores for polymeric thin films and optical waveguides and devices comprising the same
US7307173B1 (en) Pyrroline chromophores
JP2004508430A (en) Hyperpolarizable organic chromophore
JP5826206B2 (en) Nonlinear optical material and nonlinear optical element using the same
CN1349651A (en) Method for doping a polymer
KR101758393B1 (en) Photosensitive resin composition, method of forming pattern, color filter, and display device
CN1829939A (en) Second order nonlinear optical chromophores, polymers containing same, and electro-optic devices therefrom
EP1268586B1 (en) Polymers, processes, compositions, adhesives, uses, products
CN1887883A (en) V-type conjugated light-absorbing organic salt compound and use thereof
CN1425018A (en) Novel chromophores for polymeric thin films and optical waveguide and devices comprising the same
Brand et al. Functionalized hexa-peri-hexabenzocoronenes: stable supramolecular order by polymerization in the discotic mesophase
Zhang et al. The preparation of two-dimensional spindle-type chromophores for second-order nonlinear optical materials
Surampudi et al. Apical functionalization of chiral heterohelicenes
Jin et al. Color-tunable electroluminescent polymers by substitutents on the poly (p-phenylenevinylene) derivatives for light-emitting diodes
JP7025531B2 (en) Sulfonium salt photoinitiator, its production method, photocurable composition containing it and its application
CA2505881A1 (en) Second order nonlinear optical chromophores, polymers containing same, and electro-optic devices therefrom
Zhang et al. Highly electron-donating 3, 3′-Diaryl-1, 1′-bi (isobenzofuran) s synthesized by photochemical exocyclic [2+ 2+ 2] cycloaddition
CN103304721A (en) Polymethacrylate crosslinkable electro-optic polymer system and synthesis method and application thereof
CN1513011A (en) Thiophenes and polymers derived therefrom
JPH02287516A (en) Organic nonlinear optical material
JP3175163B2 (en) Novel pyrrole monomer, its production method and functional polymer membrane
JPH09151171A (en) Organic fluorine compound
JP3837463B2 (en) Second-order nonlinear optical material
JP2021134186A (en) Novel strong acid and use thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication