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EP0348497A1 - Materiau optique non lineaire contenant un compose hemicyanine et son procede de fabrication - Google Patents

Materiau optique non lineaire contenant un compose hemicyanine et son procede de fabrication

Info

Publication number
EP0348497A1
EP0348497A1 EP89902199A EP89902199A EP0348497A1 EP 0348497 A1 EP0348497 A1 EP 0348497A1 EP 89902199 A EP89902199 A EP 89902199A EP 89902199 A EP89902199 A EP 89902199A EP 0348497 A1 EP0348497 A1 EP 0348497A1
Authority
EP
European Patent Office
Prior art keywords
ethenyl
phenyl
nonlinear optical
formula
methylpyridinium
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Withdrawn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
EP89902199A
Other languages
German (de)
English (en)
Inventor
Dieter Dorsch
Bernhard Rieger
Eike Poetsch
Gerd Marowsky
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0348497A1 publication Critical patent/EP0348497A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3611—Organic materials containing Nitrogen
    • G02F1/3612—Heterocycles having N as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/12—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system having one nitrogen atom as the only ring hetero atom
    • C09B44/126—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system having one nitrogen atom as the only ring hetero atom in a six-membered ring, e.g. pyrridinium, quinolinium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • Nonlinear optical material which contains a hemicycline compound and process for its production.
  • the invention relates to nonlinear optical .Materials containing amphiphilic hemicyanines and polymers which contain the corresponding chromophores covalently bound, a process for their preparation and their use as nonlinear optical media.
  • Nonlinear optics deals with the interaction of electromagnetic fields in various media and the associated creation of new fields with changed properties.
  • Electro-optical switches, frequency and intensity control in laser technology, holography and the areas of information processing and integrated optics are areas of application for materials with non-linear optical properties
  • 3rd order are suitable for the production of purely optical switches and thus as waveguides for the construction of purely optical computers.
  • inorganic substances such as potassium dihydrogen phosphate or lithium niobate show non-linear optical properties.
  • all of these connections have various disadvantages.
  • inorganic compounds In addition to • insufficient values for second order dielectric susceptibility, inorganic compounds often lack sufficient photostability when treated with high light intensities or are difficult to manufacture and process.
  • Organic compounds of the nitroaniline type are known from Garito et al., Faser Focus 8 (1982) and EP-0091-838. Their relatively good values for photochemical stability and dielectric susceptibility are second However, order goes hand in hand with poor crystallizability and poor mechanical stability. In particular, the production of thin layers, as required by the integrated optics, does not succeed with these materials.
  • R 2 equal to CH_ based on Langmuir-Blodgett films
  • EP-A2-203780 discloses multilayer LB films which consist of alternating layers of two
  • R 1 and R2 is H or lower alkyl and R3 is a long alkyl chain, in the second R 2 and R3 is lower alkyl and
  • R is a long alkyl chain. Furthermore, G.H. Cross et al. in J. Opt. Soc. At the. B / Vol. 4, No. 6, June 1987
  • the materials still have unsatisfactory nonlinear optical properties and do not adequately meet the requirements placed on commercial use as nonlinear optical media.
  • the invention therefore relates to nonlinear optical materials, characterized in that they contain at least one compound of the formula I,
  • W, X, Y and 2 each independently CH,
  • R 2, R3 j ⁇ each independently
  • R each independently of one another H and / or C -, - C 6 alkyl and
  • the invention also relates to nonlinear optical materials containing at least one polymeric component, characterized in that the chromophore is covalently bonded to the polymer chain in accordance with formula I, optionally via a spacer.
  • the invention furthermore relates to a process for the production of nonlinear optical materials, characterized in that a layer of polymerizable compounds containing a chromophore of the formula I, optionally in a mixture with other polymerizable compounds, is applied to a substrate and then polymerized, or that the compounds are first polymerized and the polymer is subsequently applied as a film to the substrate, the chromophores of the polymer applied to the substrate being oriented non-centrosymmetrically.
  • the invention relates to the use of the nonlinear optical materials according to the invention as optical media in electronics or as organic substrates in film and fiber technology and in nonlinear optical arrangements.
  • W, X, Y and Z each independently represent CH, C-alkyl (C -, - C 6 ) or C-halogen.
  • C -.- C accordingly means methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-methylethyl, 2-methylpropyl, 2-methylbutyl, 2-ethylpropyl or 2-ethylbutyl, halogen, for example fluorine, chlorine or bromine .
  • One or two of the radicals W, X, Y or Z also denote N, preferably X and / or Z.
  • the nitrogen-containing six-membered ring preferably denotes an unsubstituted or substituted pyridine, pyrimidine or 1,3,5-triazine ring, particularly preferably a pyridine ring.
  • a each independently of one another preferably denotes a single bond or Furthermore, preference is also given to compounds in which A is -C ⁇ C- or
  • Q each independently of one another is preferably unsubstituted or by at least one alkyl radical having 1 to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-methylethyl, 2-methylpropyl, 2-methylbutyl, 2 -Ethylpropyl or 2-ethylbutyl and / or 1,4-phenylene substituted by halogen, in particular fluorine or chlorine, in which a CH group can also be replaced by N.
  • Q particularly preferably means 1,4-phenylene which is unsubstituted or substituted in the stated preferred manner.
  • n is preferably 1, 2 or 3.
  • R is preferably -, - C 4 alkyl, that is methyl, ethyl, propyl, 2-methylethyl and butyl.
  • R 4 is preferably each independently of the other
  • C 1 ⁇ C 4 Aiky 1 ' so for example methyl, ethyl, propyl, 2-methylethyl and butyl.
  • V ⁇ means a compatible anion such as a halide, methoxysulfonate, p-toluenesulfonate or another suitable anion of an inorganic or organic acid.
  • CH 3 OS0 3 , CH 3 - O -S0 3 ⁇ , Br ⁇ , I ⁇ , BF 4 ⁇ and Re0 4 ® are particularly preferred.
  • the chromophores corresponding to formula I have excellent nonlinear optical properties. It is immaterial whether they are compounds of the formula I or covalently bound to a polymer matrix are used according to the invention.
  • the presence of a donor-acceptor system in the form of the present hemicyanm structure with two long alkyl radicals R 2 and R3 is of importance.
  • the quaternized nitrogen-containing six-membered ring acts as the acceptor and the amino group acts as the donor.
  • the materials according to the invention can be used in the form of LB layers, applied to a substrate, according to the invention.
  • a non-centrosymmetrically oriented polymer film (non-centrosymmetry of the chromophores) can be produced on a substrate, for example glass or another suitable material, by polymerizing a polymerizable compound containing a chromophore according to formula I, then an LB mono - Layer of the polymer is produced according to known and conventional methods, preferably on a water surface, and then applied to the substrate (M. Sugi, "Langmuir-Blodgett films - a course towards molecular electronics: a review", J Mol. Electron.
  • the structure of the polymer structure is also not critical.
  • Polystyrenes, polyesters, polysiloxanes, poly (meth) acrylates, poly (meth) acrylamides and their copolymers and polymer mixtures or other polymer materials can be used.
  • those compounds of the general formula I or those polymers which contain a chromophore corresponding to the formula I covalently bonded are preferably used as nonlinear optical materials in which R 1, R 2,
  • R 3 , R 4 , R 5 , W, X, Y, A, Q, n and V ⁇ have the meanings given above.
  • Preferred compounds of the formula I and compounds of the formula I whose chromophores are covalently bonded to a polymer chain are thus those of the sub-formulas Ia to Ic
  • Het is equal to Pyr ⁇ V ⁇ , in which Pyr denotes an unsubstituted or, in the stated preferred manner, substituted pyridine, pyrimidine or triazine ring.
  • Pyr denotes an unsubstituted or, in the stated preferred manner, substituted pyridine, pyrimidine or triazine ring.
  • compounds of the sub-formula Ial to Ia3 are accordingly very particularly preferred.
  • R 1 -Het-C (R 4 ) C (R 4 ) -Phe-NR 2 R 3 Ia2
  • Phe means 1,4-phenylene which is unsubstituted or, preferably, substituted, in which one or two CH groups can also be replaced by N.
  • the preferred compounds of the sub-formulas Ib include those of the sub-formulas Ibl to Ib6
  • the preferred compounds of sub-formula Ic include those of sub-formulas Icl to Ic7
  • the compounds of the general formula I can be prepared by standard processes or organic chemistry.
  • reaction conditions can be found in the standard works of preparative organic chemistry, e.g. HOUBEN-WEYL, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, ORGANIC SYNTHESES, J. Wiley, New York - London - Sydney, or HETEROCYCLIC COMPOUNDS, Vol. 14, J. Wiley, New York - London - Sydney.
  • C (R 4) C (R4) means, for example, can be prepared by condensing alkyl compounds with a corresponding aldehyde or ketone in a conventional manner. The condensation is advantageously under Addition of a dehydrating agent such as acetic anhydride, a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonium acetate or piperidinium acetate.
  • a dehydrating agent such as acetic anhydride
  • a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonium acetate or piperidinium acetate.
  • an inert solvent such as hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene, has also proven to be expedient.
  • the reaction temperature is usually between 0 ° and 250 ° C, preferably between 20 ° and 150
  • alkyl six-ring aza compounds and aldehydes or ketones used as the starting material are known or can be obtained in analogy to the known by customary methods.
  • an aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. 12_ (1979) 146).
  • Suitable aryl halides are, for example, chlorides, bromides and iodides, in particular bromides.
  • the tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents.
  • Examples of palladium catalysts include its salts, in particular Pd (II) acetate organic phosphorus (III) compounds such as tri-l-phosphines.
  • suitable solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or toluene.
  • aryl halides and olefins used as starting materials are commercially available in many cases or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.
  • Aryl halides can also be reacted with aryltin compounds to couple aromatics. These reactions are preferred with the addition of a catalyst such as e.g. of a palladium (O) complex in inert solvents such as hydrocarbons at high temperatures, e.g. in boiling xylene, carried out under protective gas.
  • a catalyst such as e.g. of a palladium (O) complex in inert solvents such as hydrocarbons at high temperatures, e.g. in boiling xylene, carried out under protective gas.
  • the polymers according to the invention contain at least one chromophore corresponding to the formula I, optionally covalently bound to the polymer chain via a spacer.
  • the linkage to the polymer main chain is possible at each carbon atom of a compound of formula I, optionally via a spacer.
  • the terminal linkage is particularly preferred, i.e. on a terminal C atom in R 1, R2 or R3 without an additional spacer.
  • Particularly preferred polymers are poly (meth) acrylates and poly (meth) acrylamides.
  • Suitable spacers are in particular alkylene groups with 2 to 30 carbon atoms, which are linear or branched and in which one or more CH groups can be replaced by -0-, -S- and / or -NR -.
  • spacers can be considered as spacers:
  • Preferred polymers according to the invention are prepared by reacting correspondingly substituted alcohols or amines with (meth) acrylic acid or their reactive derivatives with subsequent polymerization, under reaction conditions which are customary per se and known to the person skilled in the art.
  • the monomers are also the subject of the invention.
  • C - to C 2Q - preferably C. to Cg alkyl esters of acrylic acid and / or methacrylic acid, mixtures of these esters and mixtures of the esters mentioned with acrylonitrile, methylacrylonitrile, styrene, 4-methylstyrene, acrylic and / or methacrylamide.
  • acrylates and methacrylates mentioned of alkanols having up to 8 carbon atoms are preferred.
  • polymers which contain halogen substituents, preferably bromine or iodine, in the side chains can also be reacted with the pyridine derivatives (without R) on which the formula I is based.
  • the homo- or copolymers according to the invention are obtained in which the chromophore is preferably terminally linked to R with the polymer structure.
  • the halogen-substituted starting polymers can be obtained by homopolymerizing halogenated monomers or by copolymerizing them with preferably the comonomers mentioned.
  • the polymers are prepared by known processes, preferably by free-radical polymerization.
  • a large number of known initiators are suitable for triggering the polymerization, for example in Pappas (ed.), UV Curing: Science and Technology, Technology Marketing Corp., Stamford, CT, 1978, or in Ocian, Principles of Polymerization, McGraw- Hill, New York.
  • thermally decaying, free radical initiators are azoisobutyronitrile (AIBN) or per compounds such as potassium persulfate, dibenzoyl peroxide and cyclohexanone peroxide, for initiators decaying through the action of radiation, such as benzophenones such as Michler's ketone [4,4'-bis (dimethylamino) benzophenone ], 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzophenone, p-chlorobenzophenone, benzophenone; Anthraquinones such as, for example, anthraquinone, 2-chloroanthraquinone, 2-alkylanthraquinones; Xanthones such as 2-halogen xanthones or 2-alkyl xanthones; Thioxanthones such as 2-chlorothioxanthone, 2-alkylthioxanthones;
  • the ethylenically unsaturated monomers can be reacted in the presence of additives.
  • organic amines, phosphines, alcohols and / or thiols can be added as reaction accelerators.
  • Suitable are e.g. primary, secondary and tertiary aliphatic, aromatic, araliphatic or heterocyclic amines, e.g. are described in U.S. Patent No. 3,759,807.
  • amines examples include butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, di-cyclohexylamine, triethanolamine, N-methyldiethanolamine, phenyldiethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, p-dimethylamino-benzoic acid - Butyl benzoate, 4,4'-bis-dimethylamino-benzophenone (Michler's ketone) or 4,4'-bis-diethylamino-benzophenone.
  • Tertiary amines such as, for example, trimethylamine, tri-isopropylamine, tributylamine,
  • N-methyl-diethanolamine N-butyl-diethanolamine, tris
  • Trialkylphosphines, secondary alcohols and thiols are also suitable as reaction accelerators.
  • Small amounts of light stabilizers such as, for example, benzophenone derivatives, benzotriazole derivatives, tetraalkylpiperidines or phenyl salicylates, can also be added.
  • organic additives such as thixotropic agents, leveling agents, binders, lubricants, matting agents, plasticizers, wetting agents, silicones for improving the surface properties, anti-floating agents or small amounts of solvents are suitable as an additive to the ethylenically unsaturated monomers.
  • the photopolymerization is carried out according to methods known per se by irradiation with light or UV radiation in the wavelength range from 250 to 500 nm, preferably from 300 to 400 nm.
  • Sunlight or artificial emitters can be used as radiation sources. Advantages are e.g. High-pressure, medium-pressure or low-pressure mercury vapor lamps, xenon and tungsten lamps; Laser light sources can also be used.
  • high-energy radiation such as, for example, X-ray, electron, neutron and other nuclear radiation
  • X-ray, electron, neutron and other nuclear radiation is suitable for triggering the polymerization, the amount of photoinitiator added usually being able to be reduced or dispensed with entirely.
  • the thermal polymerization is achieved, for example, by treatment using ultrasound or microwaves or by the action of IR radiation.
  • Table 1 shows a comparison of values of the molecular second order hyperpolarizabilities ( ⁇ ) between known compounds and Example 1 according to the invention.
  • ⁇ molecular second order hyperpolarizabilities
  • the compounds of the formula I according to the invention have orders of magnitude better than the already known hemicyanines such as (1) and that even higher ß values than for the merocyanines ( 3) and (4) can be achieved.
  • the hemicyanine dyes according to the invention also offer considerable application advantages over the merocyanines. Because of their high basicity, the merocyanines are already protonated by the action of atomospheric carbon dioxide and water and structurally change into the less polarizable phenol form. In this form, however, the merocyanines have a much smaller ß value than in the phenolate form (3 or 4) (see Table 1).
  • nonlinear optical arrangements By applying the compounds or polymer materials according to the invention to a substrate in dissolved or liquid form by, for example, painting, printing, dipping or spin coating, nonlinear optical arrangements are obtained. Furthermore, they can also develop their nonlinear optical properties in powder form, as inclusions in other molecular assemblies, such as, for example, polymers, clathrates, solid solutions, as single crystals or solutions.
  • the materials according to the invention thus open up a wide field of application. They are particularly suitable in the field of integrated optics, for example in sensor and communications technology for frequency doubling of laser light, for producing directional couplers, switching elements, modulators, parametric amplifiers, waveguide structures and the like.
  • a solution of 10.0 g of 1,4-dimethylpyridinium iodide (available from 4-methylpyridine and methyl iodide), 26.5 g of 4- (N, N-dioctadecylamino) benzaldehyde (available from Vilsmeier formylation of N, N-dioctadecylaniline) and 4.2 ml of piperidine are dissolved in 100 ml of ethanol and heated to boiling for 6 hours. After cooling, the precipitate formed is filtered off and then recrystallized twice from toluene. Red crystals of melting point 228-229 ° C. are obtained.
  • a solution of 4.00 g of poly (methyl methacrylate-co-4-iodide butyl methacrylate) (obtainable by free-radical polymerization of methyl methacrylate and 4-iodobutyl methacrylate in a molar ratio of 9: 1 in toluene as solvent and azobisisobutyronitrile as initiator) and 2.88 g of Compound la in 20 ml of N-methylpyrrolidin-2-one is stirred at 80 ° C. for 8 hours.
  • the polymer is precipitated from methanol. A deep red polymer is obtained.
  • the polymer is then transferred to a quartz substrate as an LB monolayer. Good values for the non-linear second order susceptibility are obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

Des hémicyanines amphiphiles ayant la formule (I) et des matériaux polymères qui contiennent un chromophore lié par covalence selon la formule (I), dans laquelle W, X, Y, Z, A, Q, n, R1, R2, R3 et V ont la signification décrite dans la première revendication, sont utiles comme milieux optiques non linéaires.
EP89902199A 1987-12-23 1988-12-07 Materiau optique non lineaire contenant un compose hemicyanine et son procede de fabrication Withdrawn EP0348497A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873743833 DE3743833A1 (de) 1987-12-23 1987-12-23 Amphiphile hemicyanine
DE3743833 1987-12-23

Publications (1)

Publication Number Publication Date
EP0348497A1 true EP0348497A1 (fr) 1990-01-03

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EP89902199A Withdrawn EP0348497A1 (fr) 1987-12-23 1988-12-07 Materiau optique non lineaire contenant un compose hemicyanine et son procede de fabrication

Country Status (6)

Country Link
EP (1) EP0348497A1 (fr)
JP (1) JPH02503005A (fr)
KR (1) KR900700570A (fr)
DD (1) DD276487A5 (fr)
DE (1) DE3743833A1 (fr)
WO (1) WO1989005843A1 (fr)

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US5045364A (en) * 1990-05-18 1991-09-03 At&T Bell Laboratories Nonlinear optical devices and methods
FR2681321B1 (fr) * 1991-09-18 1995-03-31 France Telecom Derive de la pyridine ou de la quinoleine, materiau polymere de ce derive utilisable en optique non lineaire et son procede de preparation.
FR2686162B1 (fr) * 1992-01-13 1995-09-22 Commissariat Energie Atomique Modulateur spatial de lumiere a adressage optique.
GB9211238D0 (en) * 1992-05-27 1992-07-08 Ashwell Geoffrey J Optically non-linear materials
GB9316662D0 (en) * 1993-08-11 1993-09-29 Ashwell Geoffrey J Optically non-linear materials (2)
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WO1989005843A1 (fr) 1989-06-29
DE3743833A1 (de) 1989-07-06
JPH02503005A (ja) 1990-09-20
DD276487A5 (de) 1990-02-28
KR900700570A (ko) 1990-08-16

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