EP1290000A1 - Nouveaux chromophores de films minces polymeres et guides d'ondes optiques, et dispositifs renfermant ceux-ci - Google Patents

Nouveaux chromophores de films minces polymeres et guides d'ondes optiques, et dispositifs renfermant ceux-ci

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Publication number
EP1290000A1
EP1290000A1 EP01937449A EP01937449A EP1290000A1 EP 1290000 A1 EP1290000 A1 EP 1290000A1 EP 01937449 A EP01937449 A EP 01937449A EP 01937449 A EP01937449 A EP 01937449A EP 1290000 A1 EP1290000 A1 EP 1290000A1
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EP
European Patent Office
Prior art keywords
substituted
unsubstituted
compound
group
cyclohexyl
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.)
Withdrawn
Application number
EP01937449A
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German (de)
English (en)
Other versions
EP1290000A4 (fr
Inventor
Mingqian He
Thomas M. Leslie
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Corning Inc
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Corning Inc
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Filing date
Publication date
Priority claimed from US09/595,221 external-priority patent/US6584266B1/en
Application filed by Corning Inc filed Critical Corning Inc
Priority to EP07100800A priority Critical patent/EP1772459A3/fr
Priority to EP07100799A priority patent/EP1772458A3/fr
Publication of EP1290000A1 publication Critical patent/EP1290000A1/fr
Publication of EP1290000A4 publication Critical patent/EP1290000A4/fr
Withdrawn legal-status Critical Current

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    • 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

Definitions

  • the present invention relates to chromophores which can be used in the preparation of polymeric thin films for waveguide media, and to optical waveguides and devices comprising the chromophores.
  • Thin films of organic or polymeric materials with large second order nonlinearities in combination with silicon-based electronic circuitry can be used in systems for laser modulation and deflection, information control in optical circuitry, as well as in numerous other waveguide applications.
  • novel processes through third order nonlinearity such as degenerate four-wave mixing, whereby real-time processing of optical fields occurs, have utility in such diverse fields as optical communications and integrated circuit fabrication.
  • the utility of organic materials with large second order and third order nonlinearities for very high frequency application contrasts with the bandwidth limitations of conventional inorganic electrooptic materials currently in use.
  • the present invention is directed, in part, to compounds which can serve as chromophores in, for example, thin films for optical waveguides and optical devices. These are compounds represented by Formula I :
  • D is an electron donating group
  • B comprises at least one bivalent ring
  • R 2 and R 3 each, independently, are selected from the group consisting of substituted or unsubstituted C 2 -C ⁇ o alkenyl, substituted or unsubstituted C 2 - o alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, substituted or unsubstituted cyclohexyl, and (CH 2 ) n -O-(CH 2 ) n where n is 1-10.
  • R 2 and R 3 can be selected from substituted or unsubstituted -Cio alkyl, provided that when R 2 and R 3 are both selected from substituted or unsubstituted C_-C ⁇ 0 alkyl the following condition
  • chromophores of the invention have Formula I' :
  • R 2 and R 3 are further characterized in that they define a ring in which * denotes a spiro junction, or where * denotes a chiral center; or R 2 and R 3 each, independently, are either, substituted or unsubstituted - o alkyl, substituted or unsubstituted C 2 - 0 alkenyl, substituted or unsubstituted C - o alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, or (CH2)n-O-(CH 2 ) n . where n is 1-10.
  • D and B have the definitions given above.
  • the chromophores comprise novel cyclic bridges comprising at least one bivalent aromatic ring. Preferred compounds of
  • D is an electron donating group
  • A is an electron withdrawing group
  • J is CH 2 , O or S
  • R 1 is -Q-C n H 2n+ ⁇ , -Q-(CH 2 ) a C encourageF 2n+ ⁇ , -Q-CH 2 OCH 2 C n F 2n+1 , -Q-CH 2 SCH 2 CC constrainF 2n+1 ,
  • n 1-10
  • a 0-10
  • Q is absent, O or S.
  • the chromophores comprise novel cyclic bridges comprising at least one bivalent or conjugated ring structure, such as an aromatic ring, and novel electron withdrawing groups.
  • Such compounds are generally represented by the structure of Formula IN:
  • D is an electron donating group
  • K is O or S
  • R is -Q-C n H 2n+1 , -Q-(CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH 2 C n F 2n+ ⁇ , -Q-CH 2 SCH 2 CC n F 2n+ ⁇ , -Q-CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S; q is 1, 2, or 3; and R 2 and R 3 each, independently, are either substituted or unsubstituted C ⁇ -C 10 alkyl, substituted or unsubstituted C 2 -C 10 alkenyl, substituted or unsubstituted C 2 -C ⁇ 0 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or un
  • R and R are further characterized in that they define a ring in which * denotes a spiro junction, or where * denotes a chiral center.
  • Other useful compounds of the invention have Formula N:
  • D is an electron donating group
  • J is CH 2 , O or S
  • R 1 is -Q-C n H 2n+ ⁇ . -Q- (CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH 2 C n F 2n+1 , -Q-CH 2 SCH 2 CC n F 2n+] , -Q-CH 2 OCH 2 CF 3 , or -Q- CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S; and R 2 and R 3 each, independently, are either H, substituted or unsubstituted C ⁇ -C ⁇ 0 alkyl, substituted or unsubstituted C 2 -C ⁇ 0 alkenyl, substituted or unsubstituted C 2 -C ⁇ 0 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substitute
  • R 2 and R 3 are further characterized in that they define a ring in which * denotes a spiro junction, or where * denotes a chiral center.
  • the present invention is also directed to optical waveguides comprising a thin film medium having Formula VI:
  • P and P' are polymer main chain units, which can be the same mer unit or different mer unit, and C is a comonomer unit where n is an integer greater than zero and n' is 0 or an integer greater than zero; S is a pendant spacer group having a linear chain length of between about 2-12 atoms.
  • M is a compound having either Formula I, Formula F, Formula II, Formula III, Formula IN, Formula IV, Formula N, or Formula V, as described above.
  • electron donating group is used synonymously with “electron donator” and refers to substituents which contribute electron density to the ⁇ -electron system when the conjugated electron structure is polarized by the input of electromagnetic energy.
  • electronegative organic compounds or substituents which attract electron density from the ⁇ -electron system when the conjugated electron structure is polarized by the input of electromagnetic energy.
  • chromophore refers to an optical compound comprising an electron donating group and an electron withdrawing group at opposing termini of a conjugated ⁇ -electron system.
  • cyclic bridge is used to refer to bivalent cyclic structures which serve to couple the electron donating and withdrawing groups.
  • the present invention is also directed to optical devices comprising the optical waveguides described above.
  • the present invention is directed, in part, to novel electro-optic chromophores which have utility in organic nonlinear optical applications such as polymeric thin films for optical waveguides and optical devices.
  • polymeric thin films are described in, for example, U.S. Patent Numbers 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, each of which is incorporated herein by reference in its entirety.
  • the inventive chromophores have several advantageous features which are not found in other known or commercially available chromophores. For example, we have found that the introduction of a chiral center, preferably in the acceptor portion of the molecule, and more preferably as a racemic mixture, greatly increases the chromophore' s solubility. We have found that solubility is enhanced the greater the structural or functional differences between R 2 and R 3 . For example, we have observed significantly enhanced solubility when one of R 2 or R 3 is a chain and the other is a ring structure; or when one is a short chain (up to three carbons), and the other is a long chain (say, C4- C18).
  • inventive acceptors While there may be other factors contributing to this improved property, we have found that one major difference between the inventive acceptors and those of the prior art is the presence of chiral centers in the inventive acceptors. It is known that the physical characteristics like melting point and solubility are different for the pure enantiomer than for the racemic mixture. Several examples of this difference exist. For example, pure chiral (D) lycine has a melting point of 218 C and is very soluble at room temperature. The racimate has a melting point of 170 C and is considered infinitely soluble in room temperature water. Also, pure enantiomers of Mandelic acid have a melting point of 133 C while the racimate has a melting pint of 120 C. (R )-(+)-Mandelonirile has a melting point of 29 C while the racimate is an oil at room temperature.
  • the chiral centers do not form a single chiral compound but rather a mixture of racemic enantiomers, which when introduced into chromophores increase the solubility of the chromophores due to a depression of the melting point.
  • inventive compounds tend to form glassy solids rather than crystalline materials. Without intending to be bound by theory, we believe that the present chemistry results in improvements in the nonlinearity of the bulk polymer because of the incorporation of a racemic chiral center in the chromophores.
  • the electro-optic chromophores of the invention exhibit thermal stability to temperatures from 260 C to 310 C. These chromophores also show great solubility in most common organic solvents and, thus, are useful when used as a guest additive in most polymer films for waveguides. In addition, under intense UV-irradiation (365 nm, dosage 3 J/cm 2 up to 13 minutes), the chromophores of the invention show no changes of the UN- NIS- ⁇ IR spectrum, which indicates that the chromophores are photostable. The chromophores also demonstrate an adjustable absorption band away from normal communications wavelengths, which can be very important for reducing optical loss at communication wavelengths.
  • the chromophores of the invention have significant three- dimensional design which can prevent chromophore-chromophore anti-parallel stacking. Because of the flexible side chain substitutions, the chromophores of the invention show significantly reduced birefringence losses. In some of the chromophores of the invention, there is unique regiospecific substitution on the bridging thiophene ring, which allows the electron acceptor to more easily access the conjugated ⁇ -system of the bridge and allows the molecule backbone to be flatter.
  • some of the preferred chromophores of the invention have hydroxyl groups on the electron donor termini in order to easily process the chromophore into hydroxyl compatible organic and inorganic polymer reactions to make soluble chromophores, polymers and copolymers, as well as can be used to make highly soluble "guest" chromophores for guest-host applications.
  • the present invention is directed, in part, to compounds which can be employed as chromophores in polymeric thin films for optical waveguides.
  • such compounds comprise novel electron withdrawing groups having Formula I:
  • D is an electron donating group.
  • Preferred electron donating groups are described in, for example, U.S. Patent Numbers 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, each of which is incorporated herein by reference in its entirety.
  • D is selected from the group consisting of, but not limited to, phenyl ring(s) substituted in the para position by, for example, amino, alkylamino, dialkylamino, dialkylanilino, 1-piperidino, 1-piperazino, 1-pyrrolidino, acylamino, hydroxyl, thiolo, alkylthio, arylthio, alkoxy, aryloxy, acyloxy, alkyl, vinyl, 1,2,3,4-tetrahydroquinolinyl, and the like.
  • the most preferred electron donating groups are substituted and unsubstituted -
  • B is a cyclic bridge which couples the electron withdrawing group and the electron donating group.
  • B is at least one bivalent ring.
  • Preferred cyclic bridges comprise one or a plurality of bivalent rings.
  • Preferred bivalent rings which can be employed as cyclic bridges in the present application are described in, for example, U.S. Patent Numbers 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, each of which is incorporated herein by reference in its entirety.
  • Ring B can be aromatic or non- aromatic.
  • B is selected from the group consisting of, but not limited to,
  • R 4 is H, OH, C ⁇ -C ⁇ 0 alkyl, alkenyl, or alkynyl, halogen, and the like.
  • R 4 can also be -Q-C n H 2n+ ⁇ , -Q-(CH 2 ) a C n F 2n+ ⁇ , -Q-CH 2 OCH 2 C n F 2n+1 , -Q-CH 2 SCH 2 CC n F 2n+ ⁇ , -Q- CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S; and q is 1, 2, or 3.
  • R 2 and R 3 each, independently, are selected from the group consisting of, but not limited to, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C 2 -C ⁇ 0 alkenyl, substituted or unsubstituted C 2 -C ⁇ 0 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, substituted or unsubstituted cyclohexyl, (CH 2 ) n -O-(CH 2 ) n where n is 1-10, and the like.
  • -Cio refers to C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , and all combinations of ranges thereof.
  • R 2 and R 3 are both selected from
  • R 2 ⁇ R 3 More preferably, R and R define a ring in which * denotes a spiro junction, or where * denotes a chiral center.
  • the substituted alkyl, alkenyl, alkynyl, carbocyclic, and heterocyclic groups can comprise one or a plurality of substituents including, for example, fluorine, chlorine, D, and the like.
  • the heterocyclic groups can comprise O, N, S, and the like.
  • the aryl groups preferably include, but are not limited to, benzyl, phenyl, fluorenyl, and naphthyl.
  • the aryl groups, carbocycles, heterocycles, and cyclohexyl can also be substituted by one or a plurality of substituents including, for example, D, halides, including fluorine, chlorine and bromine.
  • the alkylaryl groups preferably comprise - o alkyl and the substituted alkylaryl groups comprise the substitutions for the alkyl and aryl groups described above.
  • R 2 and R 3 each, independently, are selected from the group consisting of benzyl, carbocycle, heterocycle, cyclohexyl, phenyl, cycloalkyl, cycloalkenyl, and substituted phenyl. Additional moieties for R 2 and/or R 3 , independently, include, but are not limited to the following:
  • R 2 and R 3 are CH 3 and the other of R 2 and R 3 is a substituted phenyl.
  • the substituted phenyl is selected from the group consisting of, but not limited to:
  • R and R together form a ring ' structure or a substituted ring structure from 3 to 7 atoms total with 5 or 6 atoms being preferred.
  • the ring structure is substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, or substituted or unsubstituted cyclohexyl or cyclopentyl.
  • the substituted ring structure can comprise substituents including, but not limited to, halides, including fluorine, chlorine and bromine.
  • the solvent is, preferably, tetrahydrofuran (THF), 1,4-dioxane, or the like.
  • THF tetrahydrofuran
  • the alkylvinylether depicted in Scheme I is ethylvinylether, other alkylvinylethers can be used.
  • the alkylvinylether is contacted with a strong base to form a first intermediate compound.
  • the strong base has a pK a greater than the ethylinic C-H bond ⁇ to the oxygen function of the alkylvinylether.
  • the strong base is an alkyl lithium, or an alkali metal salt of an alkyl anion, including, but not limited to, t-BuLi or sec-BuLi.
  • the alkylvinylether is preferably contacted with the strong base between about -70 C and -85 C, most preferably at about -78 C.
  • the first intermediate compound is contacted with a ketone and an acid/alcohol/water solution to form a second intermediate compound.
  • a ketone and an acid/alcohol/water solution to form a second intermediate compound.
  • Numerous acid/alcohol/water solutions known to those skilled in the art can be used in the present invention.
  • the acid/alcohol water solution is preferably HCl/MeOH/H 2 O,
  • the contacting is at room temperature.
  • the pH is adjusted between 1 and 4.
  • Ci-Cio refers to Q, C 2 , C 3 , C 4 , C 5 , C 6 , C , C 8 , C 9 , C 10 , and all combinations of ranges thereof.
  • the substituted alkyl, alkenyl, alkynyl, carbocyclic, and heterocyclic groups can comprise one or a plurality of substituents including, for example, fluorine, chlorine, D, and the like.
  • the heterocyclic groups can comprise O, N, S, and the like.
  • the aryl groups preferably include, but are not limited to, benzyl, phenyl, fluorenyl, and naphthyl.
  • the aryl groups, carbocycles, heterocycles, and cyclohexyl can also be substituted by one or a plurality of substituents including, for example, D, halides, including fluorine, chlorine and bromine.
  • the alkylaryl groups preferably comprise Cj-Cio alkyl and the substituted alkylaryl groups comprise the substitutions for the alkyl and aryl groups described above.
  • R 2 and R 3 each, independently, are selected from the group consisting of benzyl, carbocycle, heterocycle, cyclohexyl, phenyl, cycloalkyl, cycloalkenyl, and substituted phenyl. Additional moieties for R 2 and/or R 3 , independently, include, but are not limited to the following:
  • R 2 and R 3 are CH 3 and the other of R 2 and R 3 is a substituted phenyl.
  • the substituted phenyl is selected from the group consisting of, but not limited to:
  • R 2 and R 3 together form a ring structure or a substituted ring structure from 3 to 7 atoms total with 5 or 6 atoms being preferred.
  • the ring structure is substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, or substituted or unsubstituted cyclohexyl or cyclopentyl.
  • the substituted ring structure can comprise substituents including, but not limited to, halides, including fluorine, chlorine and bromine.
  • a preferred compound having a ring structure formed by R 2 and R 3 comprises
  • the second intermediate compound is reacted with dicyanomethane in the presence of a second base to form the electron withdrawing group portion of a compound having Formula I.
  • the second base is preferably a metal alkoxide including, but not limited to, NaOC 2 H 5 .
  • dilute acid such as, for example, HCI, is added for neutralization of the resultant electron withdrawing group.
  • the electron withdrawing group comprises R 6 which is preferably selected from the group consisting of unbranched substituted or unsubstituted - alkyl, unbranched substituted or unsubstituted C 2 -C 4 alkenyl, unbranched substituted or unsubstituted C -C alkynyl.
  • the substituted alkyl, alkenyl, and alkynyl groups can comprise one or a plurality of substituents including, for example, fluorine.
  • R 6 is selected from the group consisting of unbranched -C alkyl, -C alkenyl, and C 1 -C4 alkynyl.
  • R 6 is CH 3 .
  • the present invention is also directed, in part, to compounds which can be employed as chromophores in polymeric thin films for optical waveguides wherein the compounds comprise novel bridge groups which couple the electron withdrawing and donating groups of the chromophore.
  • Preferred compounds of the invention have Formula II:
  • D is an electron donating group. Preferred electron donating groups are described
  • A is an electron withdrawing group.
  • Preferred electron withdrawing groups are described in, for example, U.S. Patent Numbers 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,
  • R 1 is -Q-C n H 2n+1 , -Q-(CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH 2 C n F 2n+1 , -Q-CH 2 SCH 2 CC constrainF 2n+1 ,
  • n 1-10
  • a 0-10
  • Q preferably is either absent or, when present, O or S
  • q is 1, 2, or 3.
  • R 1 is C 4 -C ⁇ 0 or fluorine substituted C 4 -C ⁇ o.
  • a compound having Formula II can be prepared using a thiophene cyclic bridge which preferably comprises Formula Nil:
  • K is O or S.
  • R 1 is -Q-C n H 2n+1 , -Q-(CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH 2 C n F 2n+ ⁇ , -Q-
  • CH 2 SCH 2 CC favorF 2n+1 , -Q-CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q preferably is either absent or, when present, O or S. Other halogens or deuterium can be used in place of F.
  • R 1 is C 4 - 0 or fluorine substituted C -C ⁇ 0 .
  • the terminal aldehyde group serves as the preferred site of reaction with electron withdrawing groups.
  • Those skilled in the art can use additional groups known to those skilled in the art to couple a bridge compound to a donor.
  • Another Z group that can be used to link a bridge compound to a donor is
  • Y " is a counter ion including, but not limited to, Br " or CI " .
  • preferred compounds of the invention have Formula IH:
  • D is an electron donating group and A is an electron withdrawing group as described above.
  • J is CH 2 , O or S.
  • R 1 is -Q-C n H 2n+1 , -Q-(CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH 2 C frustrationF 2n+1 , -Q-CH 2 SCH 2 CC n F 2l - +1. -Q-CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S. More preferably, R 1 is C 4 -C 10 or fluorine substituted C -C 1 o.
  • a compound having Formula IV can be prepared using a dihydronaphthyl cyclic bridge which preferably comprises Formula VIH:
  • J is CH 2 , O or S.
  • R 1 is H, -Q-C n H 2n+ ⁇ . -Q-(CH 2 ) a C n F 2n+ ⁇ , -Q-CH 2 OCH 2 C n F 2n+1 , -Q- CH 2 SCH 2 CC n F 2n+ ⁇ . -Q-CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S. Other halogens can be used in place of F.
  • R 1 is C 4 -C ⁇ o or fluorine substituted C 4 -C ⁇ o.
  • the terminal aldehyde or ketone group serves as the preferred site of reaction with electron withdrawing groups.
  • Z is a chemical group that is capable of being linked to a donor, as described above.
  • the present invention is also directed to compounds which can be employed as chromophores in polymeric thin films for optical waveguides wherein the compounds comprise novel bridge groups and novel electron withdrawing groups, and are represented by Formula IV:
  • R 1 is -Q-C n H 2n+ ⁇ .
  • -Q-(CH 2 ) a C n F 2n+1 , -Q-CH 2 OCH2C n F 2 n + ⁇ , -Q-CH 2 SCH 2 CC n F 2n+i , -Q-CH 2 OCH 2 CF 3 , or -Q-CH 2 SCH 2 CF 3 , where n is 1-10, a is 0-10, and Q is absent, O or S, and q is 1, 2, or 3.
  • R 1 is C 4 -C ⁇ o or fluorine substituted C -C ⁇ o- More preferred compounds of this embodiment of the invention are represented by Formula IV:
  • R 2 and R 3 are further characterized in that they define a ring in which * denotes a spiro junction, or where * denotes a chiral center.
  • R and R each, independently, are selected from the group consisting of, but not limited to, substituted or unsubstituted CrC 10 alkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C 2 -C ⁇ o alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, substituted or unsubstituted cyclohexyl, (CH 2 ) n -O-(CH 2 ) n where n is 1-10, and the like.
  • R 2 and R 3 each, independently, are selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, and substituted or unsubstituted cyclohexyl. More preferably, R 2 and R 3 each, independently, are selected from the group consisting of benzyl, cyclohexyl, and substituted or unsubstituted phenyl. More preferably, one of R 2 and R 3 is CH 3 and the other of R 2 and R 3 is a substituted phenyl. Most preferably, one of R 2 and R 3 is
  • R 2 and R 3 is CH 3 .
  • R 2 and R 3 together form a ring structure or a substituted ring structure from 3 to 7 atoms total with 5 or 6 atoms being preferred.
  • the ring structure is substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, or substituted or unsubstituted cyclohexyl or cyclopentyl.
  • the substituted ring structure can comprise substituents including, but not limited to, deuterium and halides, including fluorine, chlorine and bromine.
  • a preferred compound having a ring structure formed by R 2 and R 3 comprises
  • D is an electron donating group as described above.
  • J is CH , O or S.
  • R 1 is -Q-C n H 2n+1 , -Q-(CH 2 ) a C n F 2n+ ⁇ , -Q-CH 2 OCH 2 C n F 2n+1 , -Q-
  • R 1 is C4-C10 or fluorine substituted C 4 -C ⁇ o. More preferred compounds of this embodiment are represented by the structure of Formula V:
  • R 2 and R 3 are further characterized in that they define a ring in which * denotes a spiro junction, or where * denotes a chiral center.
  • R 2 and R 3 each, independently, are selected from the group consisting of, but not limited to, substituted or unsubstituted -C 10 alkyl, substituted or unsubstituted Qr o alkenyl, substituted or unsubstituted C 2 -C ⁇ 0 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, substituted or unsubstituted cyclohexyl, (CH 2 ) n -O-(CH 2 ) n where n is 1-10, and the like.
  • R 2 and R 3 each, independently, are selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, and substituted or unsubstituted cyclohexyl.
  • R and R each, independently, are selected from the group consisting of benzyl, cyclohexyl, and substituted or unsubstituted phenyl. More preferably, one of R 2 and R 3 is CH 3 and the other of R 2 and R 3 is a substituted phenyl. Most preferably, one of R 2 and R 3 is
  • R 2 and R 3 together form a ring structure or a substituted ring structure from 3 to 7 atoms total with 5 or 6 atoms being preferred.
  • the ring structure is substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, or substituted or unsubstituted cyclohexyl.
  • the substituted ring structure can comprise substituents including, but not limited to, deuterium and halides, including fluorine, chlorine and bromine.
  • a preferred compound having a ring structure formed by R 2 and R 3 comprises
  • D is an electron donating group as described above.
  • optical waveguides comprising polymeric this films having comprising the chromophores of the invention.
  • optical waveguides comprising a thin film medium have Formula VI:
  • P and P' are polymer main chain units, which can be the same mer unit or different mer unit, and C is a comonomer unit where n is an integer greater than zero and n' is 0 or an integer greater than zero.
  • Polymers and copolymers that may be employed in the present invention are described in, for example, U.S. Patent Numbers 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, each of which is incorporated herein by reference in its entirety.
  • the polymers of the invention can be a homopolymer or a copolymer.
  • Preferred polymers and copolymers include, but are not limited to, acrylate, vinyl carboxylate, substituted arylvinyl, vinyl halide, vinyl carboxylate, alkene, alkadiene, arylvinyl, methacrylate, vinyl chloride, vinyl acetate, vinyl ether, ethylene, propylene, isobutylene, 1-butene, isoprene, styrene, and the like.
  • the polymers of the invention comprise an external field-induced orientation and alignment of pendant side chains.
  • the polymer main chain can be a structural type such as polyvinyl, polyoxyalkylene, polysiloxane, polycondensation, and the like.
  • a polymer can be applied to a supporting substrate by conventional means, such as spin coating, dip coating, spraying, Langmuir-Blodgett deposition, and the like.
  • Thin film optical waveguide medium of the present invention after fabrication can be subjected to an external field to orient and align uniaxially the polymer side chains.
  • the polymer medium is heated close to or above the polymer glass transition temperature T g , then an external field (e.g., a DC electric field) is applied to the medium of mobile chromophore molecules to induce uniaxial molecular alignment of the chromophore polymer side chains or guests in a guest-host system parallel to the applied field, and the medium is cooled while maintaining the external field effect.
  • an external field e.g., a DC electric field
  • S is a pendant spacer group having a linear chain length of between about 2-12 atoms.
  • Pendant spacer groups that may be employed in the present invention are described in, for example, U.S. Patent Numbers 5,044,725, 4,795,664, 5,247,042, 5,196,509,
  • M is a chromophore compound having Formula I, Formula I', Formula II, Formula IH, Formula IV, Formula IV, Formula V, or Formula V, described above.
  • the present invention is also directed, in part, to optical devices comprising the optical waveguides of the invention.
  • Optical devices are described in, for example, U.S. Patent Numbers 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, each of which is incorporated herein by reference in its entirety.
  • Preferred optical devices include, but are not limited to, laser frequency converters, optical interferometric waveguide gates, wideband electrooptical guided wave analog-to-digital converters, optical parametric devices, and the like, as described in U.S. Pat. No.
  • the hydroxy ketone synthesized above (0.02 mol) was mixed with malononitrile (0.04 mol) in ethyl alcohol at 20% w/v based on malononitrile cooled in an ice bath. To this, 20 ml of 1 M NaOC 2 H 5 EtOH was added dropwise. The mixture was allowed to stir overnight. After neutralization by concentrated HCI to pH 6, the solvent was evaporated by vacuum. The residue was dissolved into CH 2 C1 2 and filtered to remove the undissolved solid. After evaporating the CH 2 C1 2 , the crude product was purified by recrystalization from ethanol to give the dicyanomethylenedihydrofuran compound (1.25 g). Alternatively, and more preferably, the hydroxy ketone synthesized above (0.02 mol) was mixed with malononitrile (0.04 mol) and potassium carbonate (0.02 mol) in THF
  • Example 8 Preparation of Highly Chlorinated Electro-Optic Polymer To a three-neck flask with l,4,5,6JJ-hexchloro-5-norbornene-2,3-dicarboxylic acid chloride (2.65 g, 6.23 mmol) and 2,3,5,6-tetrachloro-p-xylene- ⁇ -diol (1.36 g, 4.93 mmol), 2-dicyanomethylen-3-cyano-4- ⁇ 2-[E-(4-N,N-di-(2-ethanol)amino)phenylene-(3- decanyl)thien-5]-E-vinyl ⁇ -5-methyl-5-(3,4-dichlorophenyl)-2,5-dihydrofuran (1 g, 1.3 mmol) were mixed in 20 ml THF at 70 C.
  • Et 3 N (1.26 g in 15 ml THF) was added dropwise. The mixture was refluxed under Ar for 48 hours. After evaporating some of the THF, the rest of the solution was slowly dropped into MeOH (300 ml) and water (50 ml) with violent stirring. The precipitated solid was filtered, redissolved in THF and precipitated again in MeOH (300 ml). The collected solid was vacuum dried for 8 hours and weighed 4.5 g. The polymer was characterized by DSC and TGA. The T g is 152 C, and the decomposing temperature under air is 285 C.

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Abstract

La présente invention concerne, d'une part, des chromophores contenant de nouveaux groupes de retrait d'électrons et de nouveaux ponts cycliques bivalents, et, d'autre part, des guides d'ondes et des dispositifs optiques pourvus de films minces polymères qui renferment ces nouveaux chromophores.
EP01937449A 2000-06-16 2001-05-16 Nouveaux chromophores de films minces polymeres et guides d'ondes optiques, et dispositifs renfermant ceux-ci Withdrawn EP1290000A4 (fr)

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EP07100800A EP1772459A3 (fr) 2000-06-16 2001-05-16 Nouveaux chromophores pour films polymères minces et guides dýonde optiques et dispositifs les comprenant
EP07100799A EP1772458A3 (fr) 2000-06-16 2001-05-16 Nouveaux chromophores pour films polymères minces et guides dýonde optiques et dispositifs les comprenant

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US09/595,221 US6584266B1 (en) 2000-06-16 2000-06-16 Chromophores for polymeric thin films and optical waveguides and devices comprising the same
US595221 2000-06-16
US09/675,966 US6393190B1 (en) 2000-06-16 2000-09-29 Chromophores for polymeric thin films and optical waveguides and devices comprising the same
US675966 2000-09-29
PCT/US2001/015827 WO2001098310A1 (fr) 2000-06-16 2001-05-16 Nouveaux chromophores de films minces polymeres et guides d'ondes optiques, et dispositifs renfermant ceux-ci

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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 (ja) * 2008-09-08 2013-12-25 住友電気工業株式会社 非線形光学化合物、非線形光学材料及び非線形光学素子
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WO2019039530A1 (fr) 2017-08-24 2019-02-28 国立研究開発法人情報通信研究機構 Stratifié pour éléments optiques non linéaires contenant une couche de polymère électro-optique et son procédé de production
JP7182798B2 (ja) * 2018-01-30 2022-12-05 国立研究開発法人情報通信研究機構 電気光学ポリマー

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