WO1997019088A1 - Nouvelles molecules optiques non lineaires et polymeres les contenant - Google Patents

Nouvelles molecules optiques non lineaires et polymeres les contenant Download PDF

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WO1997019088A1
WO1997019088A1 PCT/US1996/017058 US9617058W WO9719088A1 WO 1997019088 A1 WO1997019088 A1 WO 1997019088A1 US 9617058 W US9617058 W US 9617058W WO 9719088 A1 WO9719088 A1 WO 9719088A1
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nonlinear optical
polymer
moiety
nitro
compound
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PCT/US1996/017058
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English (en)
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David W. Polis
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Hoechst Celanese Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • 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

Definitions

  • This invention discloses novel organic molecules that contain fused ring rigid rod moieties possessing high nonlinear optical activity, and also polymers that contain such organic moieties in their repeat units .
  • Nonlinear optical activities generally result from interaction of materials with light, and are described in terms of second order nonlinearity, third order nonlinearity, and so on.
  • An introduction to the theory and practical applications of nonlinearity, especially of organic materials, is provided by Nonlinear Optical Properties of Organic Molecules and Crystals, Volumes. 1 & 2 , edited by D. S. Chemla and J. Zyss, Academic Press, 1987.
  • organic small molecules and polymeric materials with large delocalized Il-electron systems can exhibit nonlinear optical response, which in many cases is a much larger response than that exhibited by inorganic materials.
  • organic small molecules include 2-methyl-4- nitroaniline.
  • polymers are described in Nonlinear Optical Properties of Organic and
  • nonlinear Optical Properties of Organic and Polymeric Materials referred to above .
  • organic and polymeric materials can be modified structurally to suitably optimize properties such as mechanical stability, thermo-oxidative stability, and laser damage threshold.
  • Laser damage threshold is an expression of the ability of a material to withstand high intensity laser radiation.
  • the utility of a nonlinear optical material frequently is in a device where the material is subjected to high intensity laser radiation. Unless the material is capable of withstanding such radiation, the device may fail in its intended function.
  • organic polymers can be cast as thin films by techniques well known in the ar .
  • Thin films have the advantage of better utility than single crystals in device fabrication.
  • Inorganic materials generally are single crystals.
  • Thin films of organic or polymeric materials with large second order nonlinearities in combination with silicon-based electronic circuitry have potential utilities in devices for laser modulation and deflection, information control in optical circuitry and the like.
  • Novel processes occurring through third order nonlinearity such as degenerate four-wave mixing, whereby real-time processing of optical fields occurs, have potential utility in devices that have applications in such diverse fields as optical communications and integrated circuitry.
  • Devices based on optical nonlinearity of materials are described in, for example, U.S. Patent Nos. 3,234,475; 3,395,329; 3,694,055; 4,428,873; 4,515,429; 4,583,818; and by P. W.
  • Nonlinear optical materials can be used either as small molecules in a guest-host combination or, more preferably, as a covalently linked part of organic polymers.
  • Guest-host combinations are physical mixtures of a nonlinear small molecule and a film-forming polymer. Such mixtures have the disadvantage of insufficient loading of the nonlinear material and phase separation.
  • polymer systems where the nonlinear optical moiety is covalently linked to the polymer chain avoid such disadvantages and are generally referred to as nonlinear optical polymers.
  • Nonlinear moieties can be covalently linked to a polymer in either of two ways . They may exist as part of the main chain of the polymer or as pendant side groups, examples of which are also described in the afore-mentioned U.S. Patent 5,187,234.
  • An illustrative side chain polymer is a polymer of Formula I, disclosed in U.S. Patent 4,865,430 and referred to as the "DANS" polymer hereafter:
  • moieties are ladder units containing electron donor and electron acceptor functionalities conjugatively linked via a fused rigid rod heterocyclic ring system.
  • the fused heterocyclic ring system is typically a multi- ring system, such as, for example, a 5-ring system illustrated by the benzoxazinophenoxazine moiety or the benzoxazinophenothiazine moiety.
  • the benzoxazinophenoxazine moiety is exemplified by the compounds of Formula lla, and the benzoxazinophenothiazine moiety by compounds of Formula lib, with "D" and "A" representing electron donor
  • R x and R 2 being the same or different and being independently hydrogen, a C1-C6 alkyl, a halogen or an aryl such as a phenyl or naphthyl:
  • D group examples include, but are not limited to N- (2, 2-dimethyl-3-hydroxypropyl) ; N- (4, 4-bis- (4- acetoxyphenyl) -valeroyl; N- (5, 5-bis- (4-hydroxyphenyl) - hexyl;
  • R 3 is hydrogen or a Cl — C 4 alky] q is 2 — 3
  • Examples of the A group include, but are not limited to, N0 2 , C(CN) 2 , C(H) (CN), C(H) (N0 2 ), C(H) (CF 3 ) , C(H) (S0 2 CH 3 ) and C(H) (S0 2 CF 3 ) .
  • inventive moieties possess exceptionally large N.L.O. activity, as shown by their high nonlinear optical susceptibility (" ⁇ values") .
  • the moieties are also versatile enough to form parts of the main chain of the polymer, or to form pendant side chains from a polymer chain.
  • the present invention also relates to formation of solid film media having an induced non-centrosymmetric structure using the polymers of the invention.
  • the polymers of this invention have sufficient solubility in organic solvents such as halogenated hydrocarbons, ketones, esters, amides, and the like to be cast as films, using methods known to those skilled in the art, in order to obtain films with excellent transparency.
  • transparent refers to an optical medium which is transparent or light transmitting with respect to entering light frequencies (called fundamental frequencies) as well as created light frequencies (called harmonic frequencies) which terms are well known in the art and are explained in the afore-mentioned U.S. Patent 5,187,234, as well as in Nonlinear Optical Properties of Organic Molecules and Crystals, Volumes 1 & 2, mentioned earlier.
  • the harmonic frequencies that are frequently used in device fabrication are the second harmonic ("frequency doubling") and third harmonic frequencies.
  • films made from the polymers of the invention are ideally suited for fabricating nonlinear optical devices, such as frequency doublers, optical switches, light modulators, and the like.
  • nonlinear optical devices such as frequency doublers, optical switches, light modulators, and the like.
  • the present invention discloses novel N.L.O. moieties which contain an electron donor group and an electron acceptor group conjugatively linked, asymmetrically substituted, through a fused 5-ring heterocyclic ring system such as a benzoxazinophenoxazine or benzoxazinophenothiazine, as described earlier.
  • a fused 5-ring heterocyclic ring system such as a benzoxazinophenoxazine or benzoxazinophenothiazine, as described earlier.
  • extension of ⁇ -structure through such fused ladder-type 5-ring system and its planarity should lead to a very high ⁇ -overlap while the heteroatoms contribute to a net lowering of the excited state, thereby maximizing the polarization effects in such ⁇ -systems.
  • step 1 3,5, 6, -tetrachlorobenzoquinone ("chloranil”) and 2-amino-5-nitrophenol were condensed under anhydrous conditions to form 7-nitro-1, 2,4- trichloro-3H-phenoxazine-3-one (Formula IV) .
  • This compound was purified, and then reacted with 4-amino- 3-hydroxybenzoic acid to form 3-carboxy-10-nitro-6, 13- dichlorotriphenodioxazine (Formula V) .
  • This compound was then converted to its acid chloride form (Formula VI) which had good solubility and was then reacted with sodium azide to form the carbazide (Formula VII) .
  • VII was then converted into the isocyanate (Formula VIII) by Curtiu ⁇ transformation and then hydrolyzed to yield 3-amino-10-nitro-6, 13-dichlorotriphenodioxazine
  • the 5-ring N.L.O. moieties may be incorporated into polymers, either in the main chain or as pendant side chains, depending upon, among others, the nature of the moiety, polymerization conditions and any comonomer used.
  • a main chain polymer was prepared by reacting a mixture of the bisphenol monomer of Formula XXI and 4, 4 ' -hexafluoroisopropylidene diphenol with triphosgene, under basic conditions. Incorporation of up to as much as 30 mole% of compound XXI into the polymer, a polycarbonate, could be demonstrated.
  • glycidyl methacrylate was polymerized by free radical polymerization, and compound V was grafted onto the resulting polyglycidyl methacrylate. Up to 5 mole% incorporation of compound III into the polyglycidyl methacrylate to yield the copolymer XXII was observed.
  • g refers to grams, ml to milliliters, mmole refers to millimole, °C to degrees Celsius, and 'ambient temperature' to ranges between 20-28°C.
  • Example 2 Synthesis of 3-carboxy-10-nitro-6 , 13- dichlorotriphenodioxazine: In a 3 liter 3 neck round bottom flask equipped with a reflux condenser and a mechanical stirrer were placed 7-nitro-l, 2 , 4-trichloro- 5-phenoxazine-3-one (25.5 g, 0.074 mole) , 2 liters of absolute ethanol, and 4-amino-3-hydroxybenzoic acid (13.56 g, 0.088 mole, 1.2 eq. ) . To this well stirred warming suspension was added anhydrous sodium acetate (20 g, 0.24 mole, 3.3 eq. ) in one shot and the mixture heated to reflux for 18 hours .
  • anhydrous sodium acetate (20 g, 0.24 mole, 3.3 eq.
  • Example 4 Synthesis of 3-carbazoyl-10-nitro- 6 , 13-dichlorotriphenodioxazine: In a 500 ml single neck round bottom flask fitted with a drying tube was placed 3-carboxoyl-10-nitro-6, 13- dichlorotriphenodioxazine chloride (4.2 g, 0.009 mole) and 100 ml of NMP (which had previously been dried over anhydrous sodium carbonate) . To this solution was added sodium azide (1.2 g, 2.2 eq) dissolved in a minimum amount of water:NMP (1:1 v/v) all in one shot.
  • NMP sodium azide
  • the mixture was allowed to stir overnight at room temperature and then it was poured into 3 liters of 20% aqueous sodium chloride solution in a large separatory funnel.
  • the crystalline precipitate which formed slowly settled (about 12 hrs) to the bottom of the funnel facilitating a more concentrated suspension to deliver to the collection funnel.
  • the precipitate/water suspension was then dripped onto a fine fritted funnel where the product was collected and washed several times with water. After extensive air drying the product weighed 4.2 g (essentially 100%) .
  • Example 5 Synthesis of 3-isocyanato-10-nitro- 6 , 13-dichlorotriphenodioxazine (the isocyanate compound of Formula VIII) : In a 500 ml round bottom flask equipped with a condenser and drying tube were placed 3-carbazoyl-10-nitro-6, 13-dichlorotripheno-dioxazine (4.2 g, 0.009 mole) , and 200 ml of toluene. This was heated up to reflux for 18 hrs and cooled. On cooling crystals of the isocyanate grew on the side of the flask and were collected by filtration. On air drying the product yielded 3.6 g (92%) .
  • Example 6 Synthesis of 3-amino-10-nitro-6, 13- dichlorotriphenodioxazine: In a 500 ml round bottom flask equipped with a condenser were placed 3- isocyanato-10-nitro-6, 13-dichlorotriphenodioxazine from Example 5 (1.0 g, 0.002 mole) , and 50 ml of toluene. This was heated to reflux and 50 ml of 10% sodium hydroxide solution added. An emulsion formed and there was an immediate purple/blue tinge. Heating was continued until a definite separation was seen between the layers and then the product could be isolated by a procedure involving separation and centrifugation of the aqueous layer.
  • Example 7 Synthesis of 2,5-di- (hexafluoroisopropoxy) -1,4-dichloro-benzo ⁇ uinone : In a 500 ml three neck flask equipped with a solid addition funnel, condenser, and drying tube was placed hexaflouroisopropanol (3.9g, 0.022 mole) in 200 ml of dry THF. Solid sodium (5.0 g, 0.05 mole) was then added slowly at a rate to provide gentle reflux. The addition funnel was then charged with chloranil (2.45 g, 0.01 mole) and the solids added over a 1 hour period. The addition of the chloranil resulted first in the appearance of a greenish solution which slowly decolorized to yellow.
  • Example 8 Synthesis of 7-nitro-2-chloro-1, 4- di- (hexafluoroisopropoxyl) -3H-phenoxazine-3-one : This compound was prepared in a fashion similar to that of the dichloro compound above. Crystals of the 3-ring derivative precipitated from the reaction mixture,- more was obtained from the mother liquors also. The product was recrystallized from absolute ethanol (20 ml per gram) for analysis, but the filtered product is quite pure for subsequent steps. The total yield was 4.2 g (82%, mp 181-183) .
  • Example 9 Synthesis of 3-carboxy-10-nitro- 6 , 13-di- (hexafluoroisopropoxyl) -triphenodioxazine:
  • This compound was prepared similar to that of 3- carboxy-10-nitro-6, 13-dichlorotriphenodioxazine above. The yield was 90%.
  • Example 10 Synthesis of 3-carbox ⁇ l-10-nitro- 6, 13-di (hexaflouroisopropoxyl) -triphenodioxazine chloride and then the corresponding azide: These were prepared from the acid of Example 9 by a procedure described previously for the acid chloride and the azide, under Examples 3 and 4 above (yield 2.5 g, 87%) .
  • Example 11 Synthesis of 3-carboxy-10-nitro- 6 , 13-di (hexafluoroisopropoxyl) -triphenodioxazine trifluoroacetyl amide: The synthesis of the trifluoro amide was done by in-situ decomposition of the azide of Example 10 and capture of the intermediate isocyanate by trifluoroacetic acid.
  • Example 14 Synthesis of 3-carboxy-10-nitro- 6, 13-di-t-butyltriphenodioxazine: The di-chloro-di-t- butyl quinone was converted to 3-carboxy-l0-nitro-6, 13- di-t-butyl-triphenodioxazine similar to Examples 1 and 2 in 20% yield.
  • Example 15 Synthesis of 3-carboxoyl-10-nitro- 6, 13-di-t-butyltriphenodioxazine chloride: In a 250 ml single neck round bottom flask equipped with a condenser and drying tube were placed 3-carboxy-10- nitro-6, 13-di-t-butyltripheno-dioxazine (1.3 g, 0.0027 mole) , 100 ml of toluene, and freshly distilled thionyl chloride (1.0 g, 0.08 mole, 3 eq.) .
  • Example 16 Synthesis of 3-carbazoyl-10-nitro- 6, 13-di-butyltriphenodioxazine: This was prepared similar to the dichloro compound above. In a 100 ml single neck round bottom flask fitted with a drying tube was place 3-carboxoyl-10-nitro-6, 13-di-t- butyltriphenodioxazine chloride (1.2 g, 0.0024 mole) and 15 ml of dry N-methylpyrrolidinone ("NMP”) . To this solution was added in one shot a solution of sodium azide (0.17 g, 2,2 eq) dissolved in a minimum amount of water:NMP (1:1, v/v) .
  • NMP dry N-methylpyrrolidinone
  • Example 18 Synthesis of 3-amino-10-nitro-6 , 13- di-t-butyltriphenodioxazine: In a 500 ml round bottom flask equipped with a condenser were placed 3- isocyanato-10-nitro-6, 13-di-t-butyltriphenodioxazine (0.35 g, 0.00077 mole) , and 50 ml of concentrated hydrochloric acid. This was heated to approximately
  • Example 20 Synthesis of 2- (N- (2-hydroxyethyl) - N-methylamino) -3,4,6- trichlorobenzo ⁇ uinone: In a one liter single neck round bottom flask were placed 2 , 3 , 4, 6-tetrachlorobenzoquinone (chloranil) (18.45 g, 0.075 mole) , a magnetic stir bar, and 300 ml of THF. To this vigorously stirred suspension was added N-(2- hydroxyethyl) -N-methylamine (12.39 g, 13.25 ml, 2.1 eq) dropwise. The reaction was immediate, with the solution turning a dark green color and the temperature rising slightly.
  • chloranil 6-tetrachlorobenzoquinone
  • Example 21 Synthesis of the 7-nitro-l- (N-2- hydroxyethyl) -N-methylamino) -2, 4-dichloro-3H- phenoxazine-3-one: This was prepared by a procedure described in Example 1 to yield 6 to 7 grams (40 to 50%) of the desired material which may be recrystallized from aqueous ethanol. This compound may be converted to the 5-ring N.L.O. active material by a procedure described earlier for the other 5-ring compounds .
  • Example 22 Synthesis of 4,4-bis-(4- acetoxyphenyl) -valeric acid: The synthesis of 4,4-bis- (4-acetoxyphenyl) -valeric acid was done by reacting 4, 4-dihydroxyphenyl valeric acid with acetic anhydride using sodium acetate as catalyst . Thus the dihydroxy acid was suspended in acetic anhydride (100 ml) containing sodium acetate. The mixture was brought to reflux for 2 hours, cooled, and the excess acetic acid decomposed by pouring into water. The two layers were separated and the product was dissolved in 100 ml of diethyl ether. The ether layer was washed twice with 10 percent sodium carbonate, once with water and finally with saturated sodium chloride solution followed by drying and concentration. The resulting thick oil slowly crystallized on standing to the product of high purity (yield 88 percent) .
  • Example 23 4,4-bis- (4-acetoxyphenyl) -valeroyl chloride: This compound was synthesized from the above acetate by reaction with thionyl chloride in toluene followed by concentration. Thus the acetate and thionyl chloride in toluene were refluxed for 4 hours followed by work-up resulting in a low melting solid (yield essentially quantitative) . This compound was confirmed by IR as containing no carboxylic acid and was used without further purification.
  • Example 24 Synthesis of 3-N- (4, 4-bis- (4- acetoxyphenyl) -valeroyl) -10-nitro-6 , 13- dichlorotriphenodioxazine amide: The 4, 4-bis- (4- acetoxyphenyl) -valeroyl chloride prepared above was reacted with the 5 ring nitro-amine of Example 6 by traditional routes in THF to prepare the title compound which was recrystallized from acetonitrile.
  • Example 25 Synthesis of 3-N- (5 , 5-bis- (4- hydroxyphenyl) -hexyl) -10-nitro-6, 13- dichlorotriphenodioxazine amine:
  • the amide prepared above was thoroughly dried in vacuum overnight at 50° C and placed in a pre-dried three neck 500 ml round bottom flask equipped with a nitrogen purged addition funnel and condenser with drying tube.
  • the flask was charged with 100 ml of freshly distilled THF (from sodium) and cooled in an ice bath to 5 C.
  • the addition funnel was then charged with required amount of lithium aluminum hydride in THF (1 M solution) and addition was carried out to keep the flask at a gentle boil.
  • Example 26 Copolymerization of 3-N- (5 , 5-bis- (4-hydroxyphenyl) -hexyl) -10-nitro-6 , 13- dichlorotriphenodioxazine amine with triphosgene:
  • the bisphenol monomer from Example 25(0.05g, 0.000075 mole) and 4, 4 ' -hexafluoroisopropylidene- diphenol ("6-F bisphenol-A") (1.23 g, 0.0037 mole) were dissolved in 10% aqueous NaOH (50ml) containing 0.01 mole % of tetrabutylammonium chloride.
  • triphosgene (l.lg, 0.0038 mole) dissolved in 50 ml methylene chloride. The reaction was immediate and was stirred vigorously for 4 hours. The resulting polymer was isolated by precipitation in methanol followed by water washing until the filtrate was neutral. On drying the polymer weighed 1.2 g (80%) . This represented the incorporation of 2 mole % (4%/wt) . The polymer was soluble in trifluoroacetic acid and formed clear films on a glass substrate. Polymers with higher levels of incorporation (about 30 mole%) could also be prepared. These polymers were soluble in 2- (2-ethoxy) -ethoxy ethanol at 200° C.
  • Example 27 From polyglycidyl methacryalte: Polyglycidyl methacrylate was prepared first by traditional routes. The 5 ring amino-nitro compound of Example 5 was dissolved in 1:1 NMP: chlorobenzene and then reacted with the polyglycidyl methacrylate to achieve approximately 15% by weight (7 molar percentage) incorporation into the polymer.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention porte sur de nouvelles molécules polycycliques aromatiques fusionnées à tige rigide répondant à la formule générale (II) dans laquelle D et A représentent des groupes donneurs d'électron et électroaccepteurs, respectivement, X représentant un oxygène ou un soufre. Ces composés font preuve d'activité optique non linéaire élevée. L'invention porte également sur des polymères comportant ces molécules.
PCT/US1996/017058 1995-11-21 1996-10-24 Nouvelles molecules optiques non lineaires et polymeres les contenant WO1997019088A1 (fr)

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USRE41895E1 (en) 1997-07-08 2010-10-26 Bristol-Myers Squibb Company Epothilone derivatives
US7125899B2 (en) 1997-07-08 2006-10-24 Bristol-Myers Squibb Company Epothilone derivatives
US7241755B2 (en) 1997-07-08 2007-07-10 Bristol-Myers Squibb Company Epothilone derivatives
US8921542B2 (en) 1997-07-08 2014-12-30 Bristol-Myers Squibb Company Epothilone derivatives
US8536327B2 (en) 1997-07-08 2013-09-17 Bristol-Myers Squibb Company Epothilone derivatives
USRE43003E1 (en) 1997-07-08 2011-12-06 Bristol-Myers Squibb Company Epothilone derivatives
USRE41911E1 (en) 1997-07-08 2010-11-02 Bristol-Myers Squibb Company Epothilone derivatives
USRE41893E1 (en) 1997-07-08 2010-10-26 Bristol-Myers Squibb Company Epothilone derivatives
EP0981069A1 (fr) * 1998-08-17 2000-02-23 Siemens Aktiengesellschaft Copolymères non linéaires optiquemment actifs
EP1805150A2 (fr) * 2004-10-29 2007-07-11 Third-Order Nanotechnologies, Inc. Architectures de chromophores heterocycliques
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EP1805150A4 (fr) * 2004-10-29 2009-07-15 Third Order Nanotechnologies I Architectures de chromophores heterocycliques
CN102304130B (zh) * 2004-10-29 2017-08-25 光波逻辑有限公司 杂环发色团结构
EP1805144A4 (fr) * 2004-10-29 2009-08-05 Third Order Nanotechnologies I Architectures chromophores heterocycliques
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JP2008534750A (ja) * 2005-03-31 2008-08-28 サード−オーダー ナノテクノロジーズ， インク． 新規の電子受容システムを有するヘテロ環式発色団の構造
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