WO1998021521A1 - Materiaux optiques a absorption de deux photons ou d'ordre superieur et procedes d'utilisation - Google Patents

Materiaux optiques a absorption de deux photons ou d'ordre superieur et procedes d'utilisation Download PDF

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WO1998021521A1
WO1998021521A1 PCT/US1997/020596 US9720596W WO9821521A1 WO 1998021521 A1 WO1998021521 A1 WO 1998021521A1 US 9720596 W US9720596 W US 9720596W WO 9821521 A1 WO9821521 A1 WO 9821521A1
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group
carbons
independently selected
photon
linear
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WO1998021521A9 (fr
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Seth R. Marder
Joseph W. Perry
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California Institute Of Technology
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/25—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/248—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes porphines; azaporphines, e.g. phthalocyanines

Definitions

  • the invention relates generally to materials which exhibit nonlinear absorptive properties. More particularly, the invention relates to materials which have high two-photon or higher-order absorptivities and methods for their use.
  • the exciting light is not attenuated by single-photon absorption in this case, it is possible to excite selectively molecules at a greater depth within a material than would be possible via single-photon excitation by use of a beam that is focused to that depth in the material.
  • These two advantages also apply to, for example, excitation within tissue or other biological materials.
  • multi-photon lithography or stereolithography the nonlinear scaling of absorption with intensity can lead to the ability to write features below the diffraction limit of light and the ability to write features in three dimensions, which is also of interest for holography.
  • the ability to realize many of the possible applications of two-photon or higher-order absorption by molecules rests on the availability of chromophores with large two-photon or higher-order absorption cross sections.
  • the motifs may be generally categorized as follows: a) molecules in which two donors are connected to a conjugated ⁇ (pi)- electron bridge (abbreviated "D- ⁇ -D” motif); b) molecules in which two donors are connected to a conjugated ⁇ (pi)- electron bridge which is substituted with one or more electron accepting groups (abbreviated "D-A-D” motif); c) molecules in which two acceptors are connected to a conjugated ⁇ (pi)- electron bridge (abbreviated "A- ⁇ -A” motif); and d) molecules in which two acceptors are connected to a conjugated ⁇ (pi)- electron bridge which is substituted with one or more electron donating groups (abbreviated "A-D-A” motif).
  • Figure 1 schematically illustrates an intersystem crossing from the singlet manifold of states to the triplet manifold of states according to the invention
  • Figure 2 is a graph of oxidation potentials for two series of diamines according to the invention.
  • Figure 3 illustrates a Wittig reaction scheme for synthesis of bis-donor- substituted stilbene and bis-donor-substituted diphenylpolyenes according to the invention
  • Figure 4 illustrates a reaction scheme for the synthesis of piperidine stilbenes according to the invention
  • Figure 5 illustrates a reaction scheme for the synthesis of 4-[N-(t- butoxycarbonyl)]-piperazine benzaldehyde according to the invention
  • Figure 6 illustrates a reaction scheme for the synthesis of dimethacrylate- substiruted bis-donor stilbenes according to the invention
  • Figure 7 illustrates a reaction scheme for the synthesis of bis- (dialkylamino)stilbenes substituted with benzoate esters according to the invention
  • Figure 8 illustrates a reaction scheme for the synthesis of an cyano- substituted and primary amino-substiruted stilbene according to the invention
  • Figure 9 illustrates a reaction scheme for the synthesis of an amine biotin substituted two-photon absorbing stilbene
  • Figure 10 illustrates the reaction of l,4-bis(cyanomethyl)benzene with 4- diphenylaminobenzaldehyde and 4-di- «-butylaminobenzaldehyde to form 1,4- bis(p-cyano-4-diphenylaminostyryl)benzene and l,4-bis( ⁇ -cyano-4-di- «- butylaminostyryl)benzene according to the invention;
  • Figure 11 illustrates the condensation of 1 ,4-dibromo-2,5- bis[methylene(triphenylphosphonium)]benzene dibromide, 1 ,4-dicyano-2,5- bis[methylene(triphenylphosphonium)]benzene dibromide and 4-diphenyl- aminobenzaldehyde to yield 1,4-dibromo- and l,4-dicyano-2,5-bis(4'- diphenylaminostyryl)benzenes;
  • Figure 12 illustrates a reaction scheme for the synthesis of molecules following the A-D-A motif
  • Figure 13 illustrates nonlinear abso ⁇ tion spectra of 4,4'-bis(di-n- butylamino)stilbene (squares), 4-(di-n-butylamino)-4'-(dimethylamino)diphenyl- butadiene (circles) and 4-(di-n-butylamino)-4'-(dimethylamino)diphenyl hexatriene (triangles) in toluene solution;
  • Figure 14 illustrates nonlinear abso ⁇ tion spectra of 4,4'-bis(di- «- butylamino)stilbene (squares) and 4,4'-bis(diphenylamino)stilbene (circles);
  • Figure 15 illustrates induction times for two-photon polymerization of a triacrylate monomer (SR9008) with 2 mJ, 8 ns, 594 nm pulses;
  • Figure 16 illustrates two specific examples of photodeprotecting schemes according to the invention
  • Figure 17 illustrates two-photon optical limiting in 4-(dimethylamino)-4'-
  • Figure 18 illustrates two-photon optical limiting responses of 0.01 and 0.134 M solutions of 4,4'-bis(dibutylamino)stilbene for ⁇ 5 ns, 600 nm pulses;
  • Figure 19 shows the nonlinear abso ⁇ tion peaks for 4,4'-bis-(di-n- butylamino)stilbene and 4,4'-bis-(diphenylamino)stilbene and the linear transmission of a mixture of these compounds at a total concentration of 0.1 M;
  • Figure 20 illustrates nonlinear transmission data showing enhanced two- photon abso ⁇ tion in a l-(4-dimethylaminophenyl)-10-(4-dibutylaminophenyl)- deca-l,3,5,7,9-pentane (squares) as compared to the 4,4'-bis-(di-n- butylamino)stilbene (circles).
  • bridge it is meant a molecular fragment that connects two or more chemical groups.
  • donor an atom or group of atoms with a low ionization potential that can be bonded to a ⁇ (pi)-conjugated bridge.
  • exemplary donors in order of increasing strength, are:
  • acceptor an atom or group of atoms with a high electron affinity that can be bonded to a ⁇ (pi)-conjugated bridge.
  • Exemplary acceptors in order of increasing strength, are:
  • acceptors that have accepting strength greater than C(O)R include:
  • R is as defined below in Note 3B, and X(O) indicates that the element oxygen is double bonded to the element X and * indicates the point of attachment to the ⁇ -conjugated bridge.
  • aromatic group it is meant a carbocyclic group that contains 4n+2 ⁇ electrons where n is an integer.
  • heteromatic group it is meant a cyclic group of atoms, with at least one atom within the ring being an element other than carbon, that contains 4n+2 ⁇ electrons where n is an integer.
  • chromophore it is meant a molecule or aggregate of molecules that can absorb electromagnetic radiation.
  • imultaneous it is meant that two events that occur within the period of 10" 14 sec or less.
  • excited state it is meant an electronic state of a molecule wherein electrons populate an energy state that is higher than another energy state for the molecule.
  • two-photon abso ⁇ tion it is meant the process wherein a molecule absorbs two quanta of electromagnetic radiation to reach an excited state.
  • multi -photon abso ⁇ tion it is meant a process wherein a molecule absorbs two or more quanta of electromagnetic radiation to reach an excited state.
  • optical limiting it is meant a process wherein the optical transmission of a body decreases with increasing incident optical intensity or fluence such that the intensity of fluence transmitted by the body does not exceed a prescribed level for a prescribed range of incident optical intensity or fluence.
  • a " ⁇ -conjugated bridge” contains covalent bonds between atoms that both have ⁇ bonds and ⁇ bonds formed between two atoms by overlap of their atomic orbitals (s+p hybrid atomic orbitals for ⁇ bonds; p atomic orbitals for ⁇ bonds) with two orbitals (sp 3 , sp 2 , sp) overlapping end-to-end to form a ⁇ bond lying directly between the nuclei.
  • s+p hybrid atomic orbitals for ⁇ bonds; p atomic orbitals for ⁇ bonds with two orbitals (sp 3 , sp 2 , sp) overlapping end-to-end to form a ⁇ bond lying directly between the nuclei.
  • a ⁇ -conjugated bridge is one having a formal structure consisting of double or triple bonds alternating with single bonds where the double and triple bonds are capable of further ⁇ overlap with each other.
  • Such bridges are said to be ⁇ -conjugated and include conjugated double or triple bonds.
  • the invention generally provides compositions of matter that have large two-photon or higher-order abso ⁇ tivities and in some cases large fluorescence quantum yields, leading to efficient two-photon or higher-order excited fluorescence.
  • two-photon or higher-order abso ⁇ tion we refer to the initial simultaneous abso ⁇ tion of two or more photons (also referred to as multi-photon abso ⁇ tion) without the actual population of an excited state by the abso ⁇ tion of a single photon. That is, subsequent to the initial abso ⁇ tion of two or more photons by the molecule, it is possible for the molecule to absorb additional photons from the state populated by the initial abso ⁇ tion event or from a state to which the molecule relaxes.
  • molecules having two or more electron donor groups such as amino groups or alkoxy groups
  • aromatic or heteroaromatic end groups as part of a ⁇ (pi)-electron bridge
  • D- ⁇ -D the combination referred to herein as "D- ⁇ -D” molecules
  • the strength and position of the two-photon or higher-order abso ⁇ tion of these molecules can be tuned and further enhanced by appropriate substitution of the ⁇ -electron bridge with at least one electron accepting group, such as cyano, (referred to herein as "D-A-D" molecules).
  • A- ⁇ -A molecules molecules having two or more electron acceptor groups such as formyl or dicyanomethylidene groups, connected to aromatic or heteroaromatic end groups as part of a ⁇ (pi)-electron bridge
  • A- ⁇ -A molecules exhibit unexpectedly and unusually high two-photon or higher-order abso ⁇ tivities in comparison to dyes such as stilbene, diphenylpolyenes, phenylene vinylene oligomers and related molecules.
  • the strength and position of the two-photon or higher-order abso ⁇ tion of these molecules can be tuned and further enhanced by appropriate substitution of the ⁇ -electron bridge with electron donating groups, such as methoxy, to form "A-D-A" molecules.
  • the aromaticity of the ⁇ -bridge in the electronic ground state is important in determining the energetic position of the electronic state which is responsible for multi-photon abso ⁇ tion relative to the state responsible for one-photon abso ⁇ tion.
  • having donors attached to aromatic groups or heteroaromatic groups, i.e., D- ⁇ -D and D-A-D structures is conducive to placing the highly absorbing two-photon state energetically above that of the strongly fluorescent one-photon state, which is essential for the molecule to exhibit a high multi-photon fluorescence excitation efficiency.
  • D-A-D molecules upon abso ⁇ tion of photons, charge is redistributed from the electron donor groups toward the ⁇ - electron bridge, thereby enhancing the molecules' multi-photon abso ⁇ tion characteristics.
  • A- ⁇ -A and A-D-A structures are conducive to placing the highly absorbing two-photon state energetically above that of the strongly fluorescent one-photon state.
  • A-D-A molecules upon abso ⁇ tion of photons, charge is transferred from the ⁇ -electron bridge toward the electron accepting groups, thereby enhancing the molecules' multi-photon abso ⁇ tion characteristics.
  • the combination of the intrinsically high fluorescence quantum efficiency for these molecules and the rapid relaxation of the two-photon excited molecule from the two-photon state to the lower lying fluorescent one- photon state makes the molecules according to the invention highly efficient multi- photon excitable emitters.
  • molecules according to the invention can be used for two-photon or higher-order sensitization by exploiting various photophysical or photochemical mechanisms such as energy transfer or charge transfer.
  • the two-photon or higher-order absorber may directly sensitize various reactions or may transfer energy or charge to another sensitizer which itself sensitizes a further chemical reaction.
  • any photochemical reaction which could be carried out by energy transfer or electron transfer could be performed by taking advantage of the associated benefits of two-photon or multi-photon abso ⁇ tion provided that either the Si, S , . . . S n , T ⁇ ; T 2 , . . . T ⁇ (where S refers to a singlet state and T refers to a triplet state and have the usual meaning as described in N. J.
  • Mechanisms to foster such intersystem crossing processes include, but are not limited to, the inclusion of heavy atoms with large spin-orbit coupling coefficients, the attachment of aromatic ketones to the ⁇ -bridge electronic system of the multi-photon absorbing chromophores and attachment of paramagnetic groups.
  • These new two-photon or multi-photon absorbing molecules may be used as fluorophores in microscopy, biological imaging, photodynamic therapy, pathology assays and medical diagnostics. These new two-photon or multi-photon absorbing molecules may be used as fluorophores in thin films and materials for imaging and analysis, especially in paint compositions, laminants, dental fillings or other coatings.
  • These new two-photon or multi-photon absorbers may be used for two- photon generation of charge carriers, especially in photorefractive polymers.
  • These new two-photon or multi-photon fluorophores may be used in three dimensional light emitting displays.
  • These new two-photon or multi-photon absorbers may be used in holographic recording materials involving the use of a single or two different optical wavelengths for the recording process.
  • These new two-photon or multi-photon fluorophores may be used as two- photon or multi-photon laser dyes with upconverted emission.
  • These new two-photon or multi-photon fluorophores may be used for sensing applications including, but not limited to, sensing of metal ions and other species in solution, to electric fields or changes thereof (as in measurements of membrane potentials), viscosity of the surrounding environment and changes thereof, dielectric constants of the environment and changes thereof, biologically relevant organic molecules including, but not limited to, drugs, DNA sequences, antibodies, metabolites, hormones, explosives and neurotoxins.
  • sensing relies on the fact that the fluorescence properties of these molecules, including their emission wavelength, efficiency and lifetimes, are all parameters known to be sensitive in a quantifiable manner to external perturbations.
  • These new two-photon or multi-photon absorbers may be used as fluorophores for imaging of flow fields and diffusional fronts in gels or other porous media, especially in electrophoretic gels.
  • These new two-photon or multi-photon absorbers may be used for two- photon or multi-photon optical lithography and three dimensional optical memory.
  • These new two-photon or multi-photon absorbers may be used for optical limiting and optical switching. These new two-photon or multi-photon absorbers may be used to access photochemistry that would ordinarily be enabled by single-photon abso ⁇ tion.
  • any photochemical reaction that can be carried out either by charge or electron transfer can be performed by taking advantage of the associated benefits of two-photon or higher-order abso ⁇ tion provided that the S,, S 2 or S N excited state, T,, T 2 or T N excited state (where S refers to singlet and T refers to triplet) of the molecule has sufficient energy and/or redox potential to foster the desired reaction.
  • molecules in one embodiment of the invention are that molecules "end capped" with electron donor substituents, i.e., D- ⁇ -D and D-A-D structures, have relatively low oxidation potentials, Ey 2 (in tetrahydrofuran) for the ground-state as exemplified for the series of diamines having increasing length of ⁇ -conjugated bridge in Figure 2.
  • these molecules Upon multi-photon excitation, these molecules become very strong excited state reducing agents and can therefore be used as multi-photon excited electron donors.
  • Such materials can transfer electrons to electron acceptors (which may be covalently attached to the multi-photon absorbing chromophore or could be in a region of space near the multi-photon absorbing chromophore, as would be the case in a concentrated fluid solution or solid solution) to create a radical cation, in the case of a multi-photon absorbing dye and a radical anion, in the case of the acceptor.
  • molecules "end capped" with electron accepting substituents i.e., A- ⁇ -A and A-D-A structures
  • A- ⁇ -A and A-D-A structures have relatively high electron affinities in the ground-state form.
  • these molecules upon multi-photon excitation, become very strong excited state oxidizing agents and can therefore be used as multi-photon excited electron acceptors.
  • Such materials can accept electrons from electron donors (which may be covalently attached to the multi-photon absorbing chromophore or could be in a region of space near the multi-photon absorbing chromophore as would be the case in a concentrated fluid or solid solution) to create a radical anion, in the case of a multi-photon absorbing dye, and a radical cation, in the case of the donor.
  • electron donors which may be covalently attached to the multi-photon absorbing chromophore or could be in a region of space near the multi-photon absorbing chromophore as would be the case in a concentrated fluid or solid solution
  • Such radical cations and anions may have different spectroscopic properties from their neutral counte ⁇ arts and therefore may be used as transient photochromic materials for optical limiting and optical signal processing.
  • these radical ion species generated upon multi-photon abso ⁇ tion can be chemical reactants.
  • these multi-photon absorbing materials can be used to initiate polymerization of monomers which can be polymerized either by radical or ionic mechanisms in the presence or absence of polymerization promoters, including chain transfer agents.
  • Examples of monomers which can be polymerized in these ways include, but are not limited to, vinyl monomers including acrylonitriles, acrylates, diacrylates, triacrylates, polyacrylates, styrenes, trifunctional isocyanurates substituted with acrylates, vinyl- and allyl-containing monomers, divinylbenzene and polymers which are end-capped with or have these groups attached to the carbon backbone such as polyurethanes, polyesters and polyolefins.
  • examples of polymerizable monomers may be found in G. Odian, Principles of Polymerization, Second Edition, John Wiley and Son, New York, 1981, page 181, which is inco ⁇ orated herein by reference.
  • Another feature of the invention is that the oxidation potential, reduction potential and the energy difference between the ground state and the fluorescent excited state can be precisely tuned such that the excited state reduction or oxidation potential can also be tuned.
  • Marcus using the theory for electron transfer developed by Marcus, it is possible to tune both the forward electron transfer rate and charge recombination rate (G.J. Karvaros and N.J. Turro, Chem. Rev. 86, 401-449, 1986). This tunability allows control of, for example, the initiation rate of polymerization or the time constants for generation of abso ⁇ tion changes and recovery in transient photochromic materials.
  • Another feature of the invention is that it is possible to selectively control the position of the multi-photon abso ⁇ tion peak in these molecules by controlling the substituents on the electron donor groups. For example, replacement of the alkyl groups with phenyl groups on the amine of 4,4'-diaminostilbene results in a minimal shift of the linear abso ⁇ tion edge to a longer wavelength, but a shift of the multi-photon abso ⁇ tion maximum 90 nm to longer wavelength.
  • Another feature of this invention is that it is possible to control the position of the multi-photon abso ⁇ tion peak in these molecules by controlling the number of conjugated double bonds between the two donor-substituted aromatic or heteroaromatic end groups for Class 1 compounds (described below), or between the two electron acceptor-substituted aromatic or heteroaromatic end groups for Class 2 compounds (described below). Increasing the number of double bonds leads to a considerable shift of the multi-photon abso ⁇ tion band to longer wavelength. Inco ⁇ oration of phenylene-vinylene groups between the end groups has a similar effect.
  • Another feature of the invention is that it is possible to substitute the donor groups, and in many cases the acceptor groups, with surface specific functionalities such that the molecules may self assemble on a surface to define a pattern of multi-photon absorbing chromophore. One can then use the various multi-photon induced processes described above to perform chemistry or other optical processes on a patterned substrate.
  • Another feature of the invention is that it is possible to substitute the molecule with agents, such as biotin, which allow the molecules to form complexes with reagents (such as antibodies), tissues or surfaces labeled with the protein avidin.
  • Another feature of the invention is that it is possible to substitute molecules with functional groups such as hydroxyl, cyano and amino, to bind these compounds to metal atoms or to react, for example, with the amine or hydroxyl groups with carboxylic acids, acid chlorides, sugars or aldehydes (in the case of amine functionality).
  • functional groups such as hydroxyl, cyano and amino
  • carboxylic acids, acid chlorides, sugars or aldehydes in the case of amine functionality
  • molecules according to the invention will have use as labels for a variety of media including tissue, cells, organelles, DNA sequences, proteins, sugar, tumorous tissue, blood components, and as markers for the analysis of combinatorial libraries of chemicals, Hgands, and drugs.
  • labeling of these media with multi-photon absorbing chromophores or derivatives thereof provides a mechanism to selectively excite the multi-photon absorbing chromophores without interfering abso ⁇ tion by the other (i.e., single- photon absorbing) chromophores which do not have the multi-photon abso ⁇ tion features of chromophores according to the invention.
  • This selective excitation is particularly important for the use of these molecules in biological tissue, for example, where there are many aromatic groups such as heme-containing molecules and indole-containing molecules.
  • An advantage which is gained by the efficient multi-photon abso ⁇ tion processes enabled by molecules according to the invention is that it is possible for the abso ⁇ tion to occur in a region of space whose cross sectional area is smaller than that of the diffraction-limited spot size of the exciting beam of light. This is because, for example, a two-photon process is dependent on I 2 , where I is the intensity of the exciting beam.
  • the diffraction-limited spot size for a Gaussian beam is given by:
  • compositions which can be used in accordance with the invention have the general formulas as shown below.
  • the molecules we teach have large multi-photon abso ⁇ tivities and are themselves novel.
  • the general formulas below are not inclusive of all the compositions that we teach are of use as two-photon or higher-order absorbers.
  • Other compositions which have the characteristic electronic properties, as well as other advantageous properties for a variety of applications, and methods of making and using them, will also become apparent to those with ordinary skill in the art, when one considers the examples described in the preferred embodiments.
  • Class 1 Structures Compounds where the end groups are electron donating groups
  • R a , R , Re, Rd are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ OR a ⁇ ; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ NRa2Ra3; -(CH 2 CH 2 O) a -(CH 2 ) p CONRa2Ra3;
  • R a i, Ra2, and Ra3 are independently selected from: H; a linear or branched alkyl group with up to 25 carbons;
  • R a i, Ra2, nd Ra3 can also be a functional group derived essentially from one of the 20 naturally occurring amino acids: alanine; valine; leucine; isoleucine; proline; tryptophan; phenylalanine; methionine; glycine; serine; threonine; tyrosine; cysteine; glutamine; asparganine; lysine; arginine; histidine; aspartic acid; and glutamic acid; a polypeptide; adenine; guanine; tyrosine; cytosine; uracil; biotin; ferrocene, ruthenocene, cyanuric chloride and derivatives thereof, or methacryloyl chloride.
  • derived essentially it is meant that Rai, Ra2, and R ⁇ m ay be an amino acid or a functional group that is closely related (e.g., a trivial modification of an amino acid), where is 0-10
  • R a R b , R e , R can be an aryl group of up to aromatic ring systems having 20 carbons in the aromatic ring framework (i.e., does not include carbons on the substituents), where aryl includes;
  • E can be: S; O where R A *,1 # ⁇ 8, corresponding to the subscripts in the substituents in the structure shown directly above are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; NRA#IRA#2, ORA#3J or phenyl where RA#I, RA#2, RA#3 are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; or phenyl.
  • R a R b , Re, R are independently selected from:
  • polymerizable functionalities include vinyl; allyl; 4-styryl; acroyl; methacroyl; acrylonitrile, which may be polymerized by either a radical, cationic, or anionic polymerization process.
  • polymerizable functionalities include isocyanate, isothiocyanate, epoxides such that they can be copolymerized with difunctional amines or alcohols such as HO(CH 2 ) ⁇ OH, H 2 N(CH 2 ) ⁇ NH 2 , where 1 ⁇ ⁇ ⁇ 25.
  • polymerizable functionalities include strained ring olefins such as dicyclopentadienyl, norbomenyl, cyclobutenyl where the two-photon absorbing chromophore is attached to any of the saturated carbon linkages.
  • strained ring olefins such as dicyclopentadienyl, norbomenyl, cyclobutenyl where the two-photon absorbing chromophore is attached to any of the saturated carbon linkages.
  • Such monomers can be polymerized via ring opening metathesis polymerization using an appropriate metal catalyst as would be known to those skilled in the art.
  • polymerizable functionalities include (-CH 2 ) ⁇ SiCl3; (-CH 2 ) ⁇ Si(OCH 2 CH )3; or (-CH 2 ) ⁇ Si(OCH 3 ) 3 where the two-photon absorbing monomers can be reacted with water under conditions known to those skilled in the art to form either thin film or monolithic organically modified sol-gel glasses, or modified silicated surfaces, where 0 ⁇ ⁇ ⁇ 25.
  • Rf, Rg, Rh, Ri, Rj, Rk, Rl, Rm are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ ORbi; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ NR b2 R b3 . -(CH 2 CH 2 0) ⁇ -(CH 2 ) ⁇ CONR b2 R b3 ;
  • R i, Rb2, and Rb3 can also be a functional group derived essentially from one of the 20 naturally occurring amino acids: alanine; valine; leucine; isoleucine; proline; tryptophan; phenylalanine; methionine; glycine; serine; threonine; tyrosine; cysteine; glutamine; asparganine; lysine; arginine; histidine; aspartic acid; and glutamic acid; or a polypeptide; adenine; guanine; tyrosine; cytosine; uracil; biotin; ferrocene, ruthenocene, cyanuric chloride and derivatives thereof or methacryloyl chloride.
  • derived essentially from it is meant that Rbi, Rb2, nd b3 can be an amino acid or a functional group that is closely related to an amino acid (i.e., a trivial modification of an amino acid).
  • alkyl groups set forth in the above formulas include those groups having up to 25 carbon atoms and includes both branched and straight chain alkyl groups.
  • Exemplary alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, in the normal, secondary, iso and neo attachment isomers.
  • Aryl groups referred to in the preceding formulas include aromatic hydrocarbons having up to 20 carbon atoms.
  • Exemplary aryl groups include phenyl, naphthyl, furanyl, thiophenyl, pyrrolyl, selenophenyl and tellurophenyl.
  • Acceptor Groups Containing More than Two Carbon Atoms Re, Rf, R g , Rh, Ri, Rj, Rk, Rl, Rm , can be selected from the following list of groups Al - A41 and where R n and RQ are as defined in NOTE 3B:
  • R n , RQ are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ OR gl ; -(CH 2 CH2O) a -(CH 2 ) p NRg2R g 3 -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ CONRg2R g 3; -(CH 2 CH 2 O) ⁇ -(CH 2 ) ⁇ CN
  • Rgl, Rg2, and R g 3 are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; • Rgi, Rg2, and R g 3 can also be a functional group derived essentially from one of the 20 naturally occurring amino acids: alanine; valine; leucine; isoleucine; proline; tryptophan; phenylalanine; methionine; glycine; serine; threonine; tyrosine; cysteine; glutamine; asparganine; lysine; arginine; histidine; aspartic acid; and glutamic acid; or a polypeptide; adenine; guanine; tyrosine; cytosine; uracil; biotin; ferrocene, ruthenocene, cyanuric chloride and derivatives thereof or methacryloyl chloride.
  • derived essentially from it is meant that R g ⁇ ,
  • Rg2, and R g 3 ca n be an amino acid or a functional group that is closely related to an amino acid (i.e., a trivial modification of an amino acid).
  • ⁇ is 0-10, and where ⁇ is 1- 25.
  • a a and A can be independently selected from: CHO; CN; NO 2 , and
  • A41 A42 in addition A a and A b can be independently selected from Br, Cl, and I; and where 0 ⁇ m ⁇ 10, 0 ⁇ n ⁇ 10, 0 ⁇ o ⁇ 10.
  • R a , Rb, Re, Rd are independently selected from: H; a linear or branched alkyl group with up to 25 carbons; -(CH2CH 2 O) ⁇ -(CH2) ⁇ OR a ⁇ ;
  • Rai, Ra2, and R ⁇ are independently selected from: H; a linear or branched alkyl group with up to 25 carbons.
  • R a ⁇ , Ra2, and R ⁇ can also be one of the twenty natural the amino acids; alanine; valine; leucine; isoleucine; proline; tryptophan; phenylalanine; methionine; glycine; serine; threonine; tyrosine; cysteine; glutamine; asparganine; lysine; arginine; histidine; aspartic acid; and glutamic acid; or a polypeptide; adenine; guanine; tyrosine; cytosine; uracil; biotin; ferrocene, ruthenocene, or cyanuric chloride and derivatives thereof.
  • the invention includes molecules that do not fall into Class 1 or Class 2 formulae but are within the scope of the four structural motifs described herein.
  • compositions of the invention are organic molecules having multi- photon abso ⁇ tion.
  • the compositions themselves may exist as crystals, mesoscopic phases, polymers, glasses, liquids or gases.
  • the compositions may be used alone or in combination with other crystals, mesoscopic phases, polymers, glasses liquids or gases.
  • the molecules of the present invention may, in some cases, consist of a macroscopic crystal of the molecule. Such crystals may be grown at a slow rate under equilibrium with their mother liquor by a variety of methods known to one skilled in the art. Crystals may also be grown by sublimation at reduced pressure or in some cases from a melt. In the case of vapor or vacuum deposition of crystalline, microcrystalline or amorphorous materials, it is possible using well- developed processes to form multicomponent nanocomposite materials by codeposition with other organic or inorganic materials. Another method of producing a useful optical element involves dissolving the molecule in a solvent to form a solution which can be placed in a container having the desired shape.
  • a particularly convenient and effective form of an optical element in accordance with the invention involves dispersing the multi-photon absorbing molecules in a polymeric or prepolymeric binder.
  • the multi-photon absorbing molecules can be mixed into the binder or grafted onto the polymer, prepolymer or monomer.
  • Suitable binders include polystyrene, polyacrylonitrile, polymethacrylate, poly(methyl methacrylate), poly(vinyl alcohol), copolymers of methyl methacrylate and methacrylic acid, copolymers of styrene and maleic anhydride and half ester-acids of the latter, as well as many others.
  • the polymeric binder be highly transparent so that the transparency of the molecules utilized in the practice of this invention can be advantageously employed.
  • the chromophores may still be excited by the two-photon or multi-photon abso ⁇ tion process.
  • the methods according to invention are carried out by converting a multi-photon absorbing molecule to an electronically excited state by abso ⁇ tion of at least two photons of radiation.
  • the excited state then facilitates numerous applications.
  • the molecule may be irradiated with visible, ultraviolet or infrared radiation.
  • One common form an optical element according to the invention can take is that of a Langmuir-Blodgett (LB) film.
  • LB Langmuir-Blodgett
  • a small amount of a molecule useful in the practice of this invention when spread on the surface of a liquid, forms a surface film of monomolecular thickness at the air/liquid interface.
  • an oriented monomolecular film is formed on the substrate.
  • the preparation and uses of Langmuir-Blodgett films are described in M.C. Petty, M.R. Bryce, D. Bloor, Introduction to Molecular Electronics, Edward, Arnold, London, 1995, Chapter 10, which is inco ⁇ orated herein by reference.
  • compositions according to the invention are also useful when inco ⁇ orated into solutions, prepolymers, polymers, Langmuir-Blodgett thin films, and self- assembled monolayers.
  • the compositions can be advantageously modified in such a way as to allow for variation of ease of dissolution in a variety of host media, including liquids and polymeric hosts, by changing the nature of the substituents attached to the central ⁇ -conjugated bridge framework of the molecule as well as by changing either the donors or acceptors.
  • the length and composition of the ⁇ -bridge of the molecule it is possible to control the position and strength of the two-photon (or higher-order) abso ⁇ tion and the two- photon (or higher-order) excited fluorescence.
  • compositions according to the invention may be prepared by reacting appropriate aldehydes with appropriate ylides under standard Wittig conditions.
  • the compounds can be synthesized using the McMurray reaction.
  • Figure 3 illustrates the general scheme depicting the synthesis of bis-donor stilbene and bis-donor-substituted-diphenylpolyenes by the Wittig reaction.
  • the aldehydes used in the Wittig reaction were commercially available or synthesized by methods previously reported.
  • the phosphonium salts were synthesized according to literature procedures. Other aldehdyes and phosphonium salt that could be employed in this reaction would be known to one skilled in the art of organic synthesis and with the aid of the knowledge provided in the example given below.
  • Example 1 Example 1
  • the products were either chromatographed or recrystallized in ethanol in case of the stilbene derivatives, or acetone in case of the diphenylpolyenes derivatives.
  • the yields varied between 10% and 60% for all of the reactions.
  • N,N-di-(2-t-butyldimethylsiloxy)ethyl-aniline N-phenyl diethanolamine (28.04 g, 154.7 mmol) was added at 0°C to a stirred solution of t- butyldimethylsilylchloride (58.299 g, 386.78 mmol) and imidazole (31.598 g, 464.1 mmol) in 250 mL N,N-dimethylformamide. The reaction mixture was stirred overnight at room temperature and then was added to ice water and extracted with ether. The organic layer was washed three times with brine and was dried over magnesium sulfate.
  • N-bromosuccinamide 32.116 g, 180.43 mmol was dissolved in 150 mL anhydrous N,N- dimethylformamide and added at 0°C to a stirred solution of N,N-di-(2-t- butyldimethylsiloxy)ethyl-aniline (70.37 g, 171.84 mmol) in 140 mL anhydrous N,N-dimethylformamide.
  • the flask was covered with aluminum foil and stirred overnight in the dark at room temperature. The reaction mixture was then poured into ice water and extracted with ether.
  • the reaction mixture was allowed to warm to room temperature and then brine was added and the aqueous layer was extracted with ether. The combined organic layers were washed twice with brine and dried over magnesium sulfate.
  • the crude was purified via flash chromatography over silica gel with gradual elutions from 95/5 to 80/20 (hexanes:ethyl acetate). Evaporation of solvent yielded 3.126 g (40%) of a light yellow oil.
  • the precipitate was recovered by suction filtration and the ethanol solution was diluted with 20 mL water and extracted with ethyl acetate. A solid precipitated out of the aqueous fraction and was filtered. The combined solid fractions were washed with 50/50 (methanol: water) and air dried to yield 3.485 g (57%) of a tan solid.
  • Figure 4 illustrates a reaction scheme for the synthesis of piperidine stilbenes.
  • Figure 5 illustrates a reaction for the synthesis of 4-[N-(t- Butoxycarbonyl)]-piperazine-benzaldehyde.
  • N-bromosuccinamide (4.195 g, 23.57 mmol) was dissolved in 20 mL anhydrous N,N- dimethylformamide and added to a stirred solution of N-(t-Butoxycarbonyl)-l- phenylpiperazine (6.0 g, 22.89 mmol) in 20 mL anhydrous N,N- dimethylformamide.
  • the flask was covered with aluminum foil and stirred overnight in the dark at room temperature. Water (40 mL) was added and the precipitate was filtered. The crude solid was taken up in chloroform, washed with brine, and dried over magnesium sulfate.
  • Figure 6 illustrates a reaction scheme for the synthesis of dimethacrylate substituted bis-donor-stilbenes.
  • the reaction was then stirred while cooling to room temperature and then was placed in an ice bath for 30 minutes.
  • the resulting solid was filtered and washed with 50/50 (ethano water).
  • the solid was taken up in hot tetrahydrofuran and magnesium sulfate and a small scoop of silica gel was added.
  • the solution was filtered and concentrated to a slurry.
  • Figure 8 illustrates a reaction scheme for the synthesis of an cyano substituted and primary amino substituted stilbene.
  • Figure 9 illustrates a reaction scheme for the synthesis of an amine biotin substituted two-photon absorbing stilbene.
  • Sodium ethoxide was prepared by dissolving sodium (2.40 g, 104 mmol) in absolute ethanol (200 mL). To a solution of 4-[N, N-ethyl, 2- cyanoethylamino]benzyltriphenylphosphonium iodide, (30.2 g, 52.4 mmol) and dimethylaminobenzaldehyde (7.44 g, 49.9 mmol) in absolute ethanol (400 mL), the sodium ethoxide solution was added in one portion. The mixture was heated to reflux for approximately 8h, and then cooled to 50°C before adding 400 mL of H 2 O. Upon cooling to ambient temperature, the product precipitated.
  • Example 51 Example of a copper coupling to synthesize a bithiophene derivative.
  • N,N,N,N-tetraphenyl-2,5'-diamino-2',5-bithiophene To a solution of N,N- diphenyl-2-aminothiophene (1.5 g, 6 mmol) in THF (10 mL) was added slowly a solution of H-butyllithium (2.4 mL, 6 mmol, 2.5 M in hexanes) and stirred at room temperature for 15 min. To the solution was added copper(II)bromide (1.3 g, 6 mmol). The slurry was stirred for 30 min. then quenched with water. The mixture was extracted with methylene chloride and the organic layer was dried over magnesium sulfate and the solvent was removed in vacuum.
  • H-butyllithium 2.4 mL, 6 mmol, 2.5 M in hexanes
  • 4,4'-Bis-dioctyIarmnostiIbene An oven dried 3 -necked flask was fitted with a reflux condenser and purged with nitrogen. Into the flask was placed 4,4'- dibromostilbene (1.0 g, 2.96 mmol) (synthesized by the general Wittig procedure described above), tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 ) (13.5 mg, 0.0148 mmol), o-tolylphosphine (13,5 mg, 0.044 mmol), and sodium t-butoxide (711 mg, 7.4 mmol) in 6 mL dry toluene.
  • 4,4'- dibromostilbene 1.0 g, 2.96 mmol
  • Pd 2 (dba) 3 tris(dibenzylideneacetone)dipalladium
  • o-tolylphosphine 13,5 mg, 0.044
  • Trans-4,4'- dibromostilbene (15.00 g, 44.4 mmol) was added against a counterflow of nitrogen and the reaction was stirred for an additional 15 min; sodium tert-butoxide (13.00 g, 135 mmol) was then added and m-tolylphenylamine (16.8 mL, 97.6 mmol) was added from a syringe. After 30 min at room temperature, the reaction mixture was warmed to 95°C for 24 h, at which time, the reaction appeared complete by thin layer chromatography. The reaction mixture was transferred to a separating funnel together with water (1 L) and ether (500 mL). The aqueous layer was extracted with ether until the extracts were almost colorless.
  • the cooling bath was removed and the reaction mixture was allowed to warm to room temperature over 2 h before recooling to -78° C and adding a solution 4-(m-tolylphenylamino)benzaldehyde (21.2 g, 73.8 mmol) in dry tetrahydrofuran (100 mL) dropwise.
  • the reaction mixture was allowed to warm to room temperature and then stirred at room temperature for 2 h before cautiously adding water (300 mL).
  • the mixture was extracted with diethyl ether until the extracts were almost colorless and the combined ether layers were dried on magnesium sulfate. After filtration silica gel was added and the solvent removed under reduced pressure leaving the product absorbed onto the silica.
  • the crude product was transferred to the top of a silica gel column which was eluted with toluene.
  • the first fraction was found to be an approximately statistical mixture of the geometric isomers of 3,5-bis[4-(m- tolylphenylamino)styryl]-l ,4-dimethoxybenzene. Further elution gave a trace of an unidentified material, possibly impure l-[4-(/w-tolylphenylamino)phenyl]- pentan-1-ol on the basis of its l U NMR spectrum, and then 4-(m- tolylphenylamino)benzaldehyde.
  • the cooling bath was removed and the reaction mixture was allowed to warm to room temperature over 2 h before recooling to -78°C and adding a solution 4-(r ⁇ -tolylphenylamino)benzaldehyde (1.637 g, 5.70 mmol) in dry THF (30 mL) dropwise.
  • the reaction mixture was allowed to warm to room temperature and then stirred at room temperature for 2.5 h before cautiously adding water (150 mL).
  • the mixture was extracted with diethyl ether (3 x 50 mL) and the combined ether layers were dried on magnesium sulfate.
  • the first fraction was found to be a mixture of the geometric isomers of 3,5-bis[4-(m-tolylphenylamino)styryl]-l ,4-di(/j-dodecoxy)benzene 'H NMR ( ⁇ Vacetone) £ 7.47-6.86 (m, aryl CHs), 6.65 (d), 6.56 (d), 4.12 (t), 4.05 (t), 3.77 (t), 2.25 (overlapping singlets), 2.12-1.19 (m), 0.86 (m) ⁇ .
  • the mixed isomers were dissolved in toluene (200 mL) and heated under nitrogen with a few crystals of iodine. After 3 days, the solution was passed through a silica plug.
  • l,4-Bis(4-morpholino)styryl Benzene prepared from the reaction of 4- morpholinobenzaldehyde (3.94 g, 0.02 mol) and l,4-bis(methyltriphenyl- phosphonium chloride (8.42g, 0.012 mol) and lithium/ethanol (0.296g, 0.043 mol/150 mL). Recrystallized from ethanol to yield a mixture of isomeric products, Yield 8%; Recrystallized from acetone to yield one pure isomer, Yield 11.8% m.p.
  • the cooling bath was removed, and the reaction mixture was allowed to warm to ambient temperature over a period of 2 h.
  • the mixture was diluted with water (200 mL) and stirred for lh. Upon the addition of water, a bright orange precipitate formed.
  • the precipitate (pure trans isomer of the bisaldehyde) was collected by filtration and was rinsed with diethylether (200 mL).
  • the organic layer (that contained the cis I trans isomeric mixture of the bisaldehyde) was collected and extracted with water (2x), extracted with brine (lx), and dried over Na2SO4.
  • Figure 10 illustrates the reaction of 1 ,4-bis(cyanomethyl)benzene with 4- diphenylaminostilbene and 4-di-n-butylaminobenzaldehyde to yield l,4-bis( ⁇ - cyano-4'diphenyl-aminostyryl)benzene and l,4-bis( ⁇ -cyano-4'di- «- butylaminostyryl)benzene with donor side units and acceptors on the vinylene units (see examples 72 and 73).
  • Figure 11 illustrates the condensation of l,4-dibromo-2,5- bis[methylene(triphenylphosphonium)]benzene dibromide, 1 ,4-dicyano-2,5- bis[methylene(triphenylphosphonium)]benzene dibromide and 4-diphenylaminobenzaldehyde to yield 1,4-dibromo- and l,4-dicyano-2,5-bis(4'- diphenylaminostyryl)benzenes.
  • 2,5-Bromo-l,4-bis(4'-diphenylaminostyryl)benzene was synthesized with the analogous procedure.
  • a crude product (2.354 g) was isomerized into thermodynamically more stable trans-trans isomer.
  • Toluene (10 mL) and iodine (20 mg) were added to the mixture of isomers, and the mixture was refluxed for 15h in an illuminated hood. Toluene was removed on a vacuum line, and the residue was crystallized from a dichloromethane solution upon slow diffusion of petroleum ether. Yield was 86 %. m.p. 286.5 °C.
  • Figure 12 illustrates a reaction scheme for the synthesis of A-D-A molecules according to the invention as exemplified in Examples 76-79.
  • Table 1 below presents one- and two-photon absorption data on a series of bis(dialkylamino)diphenylpolyenes with the following general structure:
  • R and R 1 are defined in the table.
  • the parameters listed are: the wavelength of the lowest energy one-photon abso ⁇ tion maximum, ⁇ (1) rnax , the wavelength of the lowest energy two-photon abso ⁇ tion maximum ⁇ (2) max , the two-photon abso ⁇ tivity ⁇ , and the one-photon fluorescence quantum yield, ⁇ fl .
  • the two- photon abso ⁇ tivities listed in the table were measured by use of a comparative two-photon excited fluorescence method employing picosecond laser pulses (of 4 ps duration) and with Rhodamine B, Fluorescein and bis(methylstyryl)benzene as standards [C. Xu and W. W. Webb, J. Opt. Soc. Am. B, 13, 481 (1996)].
  • Table 1 One-photon and two-photon optical data for bis-donor diphenylpolyenes as measured in toluene solution.
  • the two-photon abso ⁇ tivity of tr rts-stilbene which lacks bis- donor substitution, is 12 x 10 -50 u cm" s/photon at 514 nm as determined by coherent anti-Stokes Raman spectroscopy [R. J. M. Anderson, G. R. Holtom, W. M. McClain, J. Chem. Phys., 70, 4310-4315 (1979)].
  • Table 2 lists the values of ⁇ (2) max , ⁇ , and ⁇ fl for a series of bis- styryl benzene derivatives prepared in accord with the present invention.
  • the two- photon abso ⁇ tivity values were determined using a comparative nanosecond pulse two-photon excited fluorescence method with Fluorescein or Rhodamine B as standards for calibration.
  • compounds symmetrically substituted with a pair of terminal donors [i.e., D- ⁇ -D] or symmetrically substituted to form molecules according to the donor-acceptor- donor (D-A-D) or acceptor-donor-acceptor (A-D-A) motifs exhibit substantially enhanced two-photon abso ⁇ tivities compared to unsubstituted para-b ⁇ s(ortho- methylstyryl)benzene.
  • Additional measurements including transient photoinduced abso ⁇ tion measurements and picosecond time resolved pump and probe measurements confirm the presence of excited-state abso ⁇ tion induced by two-photon abso ⁇ tion, which occurs at the two-photon excitation wavelength.
  • the effective two-photon abso ⁇ tivities of the series of bis-donor diphenylpolyenes is one to two orders of magnitude larger than that measured with picosecond pulses and, in accord with the present invention, these data demonstrate utility in optical limiting applications involving nanosecond laser pulses.
  • the values of the two-photon abso ⁇ tivity obtained for the bis donor diphenylpolyenes are an order of magnitude than that of Rhodamine B.
  • Figure 13 illustrates nonlinear abso ⁇ tion spectra of 4,4'-bis(di-n- butylamino)stilbene (squares), 4-(di-n-butylamino)-4'-
  • Figure 14 illustrates nonlinear abso ⁇ tion spectra of 4,4'-bis(di- «- butylamino)stilbene (squares) and 4,4'-bis(diphenylamino)stilbene (circles).
  • ⁇ e ff is the effective two-photon abso ⁇ tivity obtained by fitting the data at low incident intensity to a pure two- photon abso ⁇ tion model
  • Y e ff is the effective three-photon abso ⁇ tivity obtained by fitting the data to a pure three-photon abso ⁇ tion model
  • Y*eff ' s tne effective three-photon abso ⁇ tivity obtained by fitting the data to a model involving two- and three-photon abso ⁇ tion and fixing the two-photon abso ⁇ tivity at the value listed as ⁇ e ff.
  • two-photon and multi-photon absorbing molecules as initiators of polymerization, specifically the use of bis-donor- substituted ⁇ -conjugated molecules as two-photon initiators.
  • Such two-photon excitable initiators have utility in two- and three-dimensional lithography applications, for example in three-dimensional optical data storage with ultrahigh storage densities (10 12 bits/cm 3 ).
  • two-photon polymerizable materials can offer over a thousand-fold increase in storage capacity.
  • Bis-donor-substituted ⁇ -conjugated molecules according to this invention exhibit large two-photon abso ⁇ tion cross sections and also possess structural features that permit them to be effective as initiators of polymerization. As has been discussed earlier, these bis-donor-substituted ⁇ -conjugated molecules exhibit large two-photon abso ⁇ tivities in the visible and the near infrared spectral regions. Another feature of these bis-donor-substituted diphenylpolyene molecules is that the donor groups also impart to them low oxidation potentials.
  • bis-donor-substituted ⁇ -conjugated molecules enable them to function as powerful reducing agents and can reduce even molecules with low electron affinities, including various polymerizable groups such as acrylate monomers. Accordingly, bis-donor-substituted ⁇ -co ⁇ jugated molecules of this invention are able to function as multi-photon excitable initiators of polymerization. Many amino-substituted phenyl-containing compounds such as aniline, are known to initiate polymerization of vinyl or acrylate monomers upon exposure to ultraviolet radiation through a charge transfer initiation.
  • the charge transfer initiation process may proceed by way of a direct charge transfer that leads to formation of initiating and propagating radical species or by way of a hydrogen abstraction reaction between members of a charge transfer complex involving the aromatic amine and the monomer that also leads to the formation of initiating and propagating radicals.
  • the rate of two-photon initiated photopolymerization depends on the two- photon excitation rate and on the quantum yield for initiation.
  • the standard expression for the rate of polymerization, R_, assuming a radical mechanism, (G. Odian, Principles of Polymerization, Second Edition, John Wiley and Son, New York, 1981, page 181) is given by
  • Ri ⁇ i (1000/N A ) ⁇ I Ni
  • ⁇ is the two-photon abso ⁇ tivity (in units of cm s photon *1 )
  • I is the photon flux (photons c ⁇ r 2 s _1 )
  • NA is Avogadro's number
  • Nj is the number density of two-photon absorbing initiators
  • ⁇ j is the quantum yield of initiation. Combining these two equations gives the rate of two-photon excited polymerization as:
  • the rate of polymerization is dependent on the magnitude of the two-photon abso ⁇ tivity of the initiator and the quantum yield of initiation, which depends both on the characteristics of the initiator and the monomer.
  • bis-donor-substituted conjugated molecules according to the invention can initiate, following two-photon excitation, the polymerization of crosslinkable liquid polyacrylate monomers.
  • Polymerization of crosslinkable monomers leads to the formation of insoluble polymeric material, such that two-photon initiated polymerization causes the deposition of an easily observable volume of solid polymer on the window of the optical cell.
  • Polymerization was generally observed when 13 mJ pulses were used but the intensity was sufficiently high that higher-order nonlinear processes may have led to polymerization. Formation of polymer was demonstrated by the characteristic pattern of infrared bands as determined by IR spectroscopy. The diminution of the peaks assigned to monomer provided further evidence for formation of polymer.
  • the induction times for polymerization initiated by two-photon excitation of selected initiator molecules with a pulse energy of 2 mJ and a wavelength of 594 nm are shown in Figure 15.
  • the molecule 4,4'-bis(dibutylamino)stilbene has a maximum two-photon abso ⁇ tivity at about 600nm and has the shortest induction time.
  • a simple alkyl substitution of ethyl for butyl on the amino group has little effect.
  • 4-(dibutylamino)-4'-(n-butoxy)stilbene has a low two-photon abso ⁇ tivity at 594 nm and has a relatively large induction time.
  • Crosslinkable monomer Tris(2-hydroxy ethyl)isocyanurate triacrylate, (Sartomer SR368)
  • Binder polymer Poly(methylmethacrylate) (PMMA)
  • This composition forms translucent yellow/orange films by spin coating or casting.
  • the ability to form polymer filaments that taper from an initial diameter ranging from millimeters to tens of microns down to final diameters of one to several microns can be of utility in providing low loss optical guided wave coupling of objects with disparate dimensions. For example, dimensional mismatch is often encountered in attempts to couple optical fibers, which can range between 10 ⁇ m to several hundred ⁇ m in diameter, to semiconductor laser diodes, which can have active areas with a cross sectional dimension of several microns or even less.
  • One feature of the two-photon initiated polymerization disclosed here is that such tapered polymer filaments or arrays of such filaments can be formed.
  • Two-photon excitation of a variety of the disclosed diphenylpolyene derivatives in the presence of acrylate monomers leads to the formation of polymer.
  • excitation leads to formation of a visually observable cross-linked polymer spot on the wall of the vessel.
  • the multi-photon absorbing materials of the invention and photopolymer compositions based on them can be used to form recording media for two or three dimensional optical data storage.
  • the advantages of using two-photon induced processes for three dimensional optical data storage are well known. Using a strongly focused optical beam it is possible to produce localized two-photon excitation in a volume of the order of 1 ⁇ m 3 , thus resulting in data storage densities of 10 12 bits/cm 3 . Additionally, using crossed optical beams, spots or sheets of data can be stored or addressed in three dimensions, albeit at lower data densities.
  • the disclosed compositions have utility in forming three dimensional optical data storage media with high recording sensitivity, due to the large two- photon abso ⁇ tivities exhibited by these materials.
  • Fluorescence of the multi-photon absorbing molecules of the present invention can be enhanced upon polymerization of the local monomer concentration relative to that of the absorber in the presence of unpolymerized monomer. Because of the charge-transfer interaction or other interactions between the two-photon excited molecule and the monomer, the fluorescence of the excited molecule is highly quenched. Upon polymerization of the monomer, the quenching ability of the monomer is eliminated and the excited-absorbers are able to emit with an unquenched efficiency. Thus, the two-photon initiated polymerization can lead to a "turning on" of the fluorescence efficiency of the polymerized spot. This feature can provide an advantage for the readout of stored bits of information because the two-photon excited fluorescence can be used to readout as opposed to other more complex, expensive and cumbersome methods such as differential interference microscopy.
  • Multi-photon absorbing molecules of the invention the compositions described above and related compositions based on other monomers or crosslinkable monomers, other polymer binders and other additives such as chain transfer agents, can be employed as multi-photon absorbing recording media for holographic recording.
  • Molecules according to the present invention that behave as two-photon initiators for polymerization of acrylates can also initiate polymerization when irradiated with wavelengths of light for which the molecules exhibit strong linear abso ⁇ tion. Thus these molecules represent a new class of near UV and visible initiators. Furthermore, from the parallel chemistry observed by single and two- photon abso ⁇ tion, one can reasonably conclude that photon absorbing molecules that are single-photon initiators will also act as two-photon initiators, providing that the two-photon state is higher in energy than the one-photon state. This can be ascertained with some degree of certainty by observing whether the molecule is fluorescent.
  • thin films of poly(triacrylate) can be prepared by excitation with low power 360 nm radiation of molecules that behave as two-photon initiators.
  • the films so prepared were identified as poly(triacrylates) by IR spectroscopy.
  • the polymerization did not take place in the presence of benzoquinone, which is a typical inhibitor for radical polymerizations.
  • the solutions turned green and the UV spectrum has an abso ⁇ tion peak at 650 nm indicative of the stilbene radical-cation which was independently characterized by spectro -electrochemistry.
  • Methylacrylate was polymerized in bulk under the absence of air by irradiation with a 450 W medium pressure mercury lamp.
  • the molecular weight of the polymer was above 400 000.
  • the polymer, characterized by IR spectroscopy showed a spectrum identical with that in the literature. After washing the polymer several times with CHCI 3 , the polymer exhibited fluorescence in the blue (-420 nm), indicating inco ⁇ orated or bound initiator.
  • the bis-dibutylaminostilbene also polymerizes methylmethacrylate, yielding a soluble polymer in chloroform or CH 2 CI 2 . Once again, the molecular weight is higher than 400 000.
  • Methylmethacrylate polymerizations were carried out in ethanol and toluene. Thus, 0.5 mL of the monomer were dissolved in 0.5 mL of the corresponding solvent in an ampoule. After adding 10 mg of bis- dibutylaminostilbene to each ampoule, nitrogen was bubbled through for 54 minutes and the ampoules were sealed. The samples were irradiated for 6 h with a 450 W medium pressure mercury lamp.
  • photoinitiators for use in biomedical or materials processing such as xanthine-based dyes
  • xanthine-based dyes are activated by single-photon excitation of their abso ⁇ tion bands in the visible spectrum.
  • These visible photoinitiators have been used for stereolithography and for in situ polymerization, but their utility for in vivo photopolymerization is limited in some applications (e.g., when fiber optics are impractical) by the small penetration depth in tissues at visible wavelengths.
  • Photoinitiators that can be activated by two-photon abso ⁇ tion of near-IR photons can provide tremendous advantages over conventional photoinitiators.
  • a complementary approach is based on the use of Forster energy transfer to create a bichromophoric photoinitiators wherein the two-photon absorber is covalently attached to a xanthine-based photo initiator (e.g., rose bengal) such that energy transfer from the two-photon absorber to the xanthine photoinitiator initiates polymerization.
  • a xanthine-based photo initiator e.g., rose bengal
  • a method for multi-photon deprotection or photodecaging of groups is described in which a multi-photon absorbing dye is attached to known photodeprotecting groups or photodecaging groups.
  • a dye can absorb two-photons or more of energy, and through an energy or charge transfer mechanism, serve to excite the attached photodeprotecting or photodecaging group, thereby inducing the deprotection of a functional group which could be a drug, neurotransmitter, metal ion or other chemical reagent.
  • Multi-Photon Absorbing Compounds According to the Invention as Optical Limiting Materials
  • Two-photon and higher-order absorbing compositions in accordance with the invention are useful in optical power or energy limiting devices. These devices can be used to protect eyes or sensors from intense optical pulses, to modify the shape of the optical output pulse from lasers, to perform a thresholding function on optical pulses for signal processing, or for optically controlled spatial light modulation.
  • Materials that exhibit nonlinear abso ⁇ tion can be used for optical limiting devices. Such materials, including excited-state absorbers, two-photon absorbers or higher-order absorbers are initially highly transparent over a certain spectral band and become more strongly absorbing in this band as the incident optical intensity or energy is increased.
  • One of the significant applications of optical limiting devices is in laser eye or sensor protection. The exposure of human eyes or sensors to intense optical pulses can lead to permanent damage or to impaired visual performance and thus presents a serious problem to those working in environments where lasers may be encountered.
  • Frequency-doubled Q-switched Nd:yttrium/aluminum/garnet lasers are very common and for these lasers (which have pulse durations of 10 ns and a wavelength of 532 nm), the ED 50 level (the exposure energy for which there is a 50% probability of producing a retinal lesion) is about 3 ⁇ J, whereas the ANSI standard maximum permissible exposure level is about 0.1 ⁇ J.
  • laser pulse energies of 1 to 100 mJ may be present, sometimes in the form of an unanticipated surface reflection off an optical component.
  • protection devices must provide nonlinear attenuation and a high linear optical transmittance, to allow high visibility under ambient working conditions.
  • molecules according to the present invention can provide a broad bandwidth optical limiting material based on a mixture of molecular two- photon or higher-order absorbers.
  • these molecules can provide optical limiting devices using a two-photon or higher-order absorbing material based on a mixture of molecular two-photon absorbers.
  • Two-photon or higher-order absorbers of the type described in this disclosure, which have large two-photon or effective two-photon abso ⁇ tivities are attractive materials for optical limiting since they can achieve large nonlinear attenuation and maintain very high linear transmittance.
  • the present invention includes a class of molecules which exhibit very strong two-photon abso ⁇ tion in a spectral region where the linear transmission is very high.
  • the present invention provides compositions of matter which have exceptionally large two-photon abso ⁇ tivities.
  • bis-amino substitution of diphenylpolyenes and related conjugated structures leads to strong two-photon bands with excitation wavelengths in the transparent region of the molecules, below the one photon abso ⁇ tion edge.
  • di-aryl substitution of the amines leads to a significant red shift of the two-photon abso ⁇ tion band but a smaller shift of the lowest one- photon abso ⁇ tion band. This provides utility in formulating broadband limiting materials which preserve transparency.
  • broadband optical limiting materials with high transparency can be obtained.
  • Large optical limiting effects have been observed with the new two-photon absorbers with large peak effective two-photon abso ⁇ tivities (e.g., > 1000 x 10 "50 cmVphoton '1 . These effects have been observed using only moderate intensity nanosecond pulses. In earlier materials, large optical limiting effects are observed only for very high intensity picosecond pulses.
  • the optical limiting by two-photon abso ⁇ tion in 4-dimethylamino- 4'- dibutylaminostilbene (MBDAS) for 605-nm, 8-ns laser pulses in a collimated beam geometry is shown in Figure 17.
  • the transmission is close to 1.0, i.e., the sample is nonabsorbing.
  • the transmission decreases and at an input energy of -2000 ⁇ J (fluence of 2 J/cm ), the transmission drops to 0.15.
  • the collimated beam geometry utilized for this measurement was one used mainly for characterizing the nonlinear transmission and not to optimize the optical limiting response.
  • a line corresponding to a transmission of 1.0 is shown for reference.
  • the sample was a 0.33M MBDAS solution in acetone with a pathlength of 1 cm.
  • the measurements were made with 605 nm, 8-ns laser pulses in a collimated beam geometry with a beam diameter of ⁇ 400 ⁇ m.
  • the spatial beam profile of the dye laser was adjusted to produce a roughly flat intensity distribution across a roughly 5-mm diameter beam.
  • the beam was passed through an 8.5X beam reducing telescope.
  • the position of the second lens in the telescope system was adjusted to produce a collimated beam over the length of the 1-cm sample cell holder.
  • the sample solutions were placed in 1 cm pathlength quartz cells; the cell holder was about 50mm from the second lens.
  • Typical maximum input energies into the samples were about 2.5 mJ.
  • the energy delivered to the samples was controlled by a series of calibrated neutral density (ND) filters.
  • ND neutral density
  • a 4% beam splitter was inserted after the ND filter holder and this reference beam was sent to a 15mm diameter silicon photodetector (equipped with appropriate ND filters to assure that the signal did not saturate the detector).
  • a similar detector system was placed 75 mm after the optical limiting samples to collect the transmitted laser signal and to measure the total transmitted energy. This large area was chosen for performing total transmitted energy measurements, since nonlinear refractive effects caused defocusing effects in the transmitted beam.
  • the detector outputs were integrated using a boxcar integrator and the integrator output was digitized and read by a PC computer. Measurements of the sample transmissions were repeated for a range of input laser energies (via the neutral density filters). The data were then analyzed by fitting them to the solution of the intensity propagation equation for two-photon abso ⁇ tion and optical limiting. For samples with no linear abso ⁇ tion, plots of 1/T versus intensity were fit to the equation:
  • T is the transmission
  • ⁇ is the effective two-photon abso ⁇ tion coefficient and is directly proportional to the molecular two-photon abso ⁇ tivity
  • L is the pathlength
  • I 0 is the incident intensity.
  • the two-photon abso ⁇ tivity of MBDAS was 13,500 x 10 " cm s/photon.
  • the response for the MBDAS solution is better than that of the best phthalocyanine excited-state absorber (chloroindium tetra-(tert- butyl)phthalocyanine) solution with a transmission of 0.95).
  • the new multi-photon absorbers according to the present invention afford several interesting advantages for optical limiting. Firstly, these molecules exhibit effective two-photon abso ⁇ tivities that are about one or more orders of magnitude higher for current state of the art materials. With such high two-photon abso ⁇ tivities, these molecules are effective in limiting nanosecond duration pulses Secondly, these molecules can have very high broadband linear transmission, since the two-photon abso ⁇ tion bands occur for photon energies well below the linear abso ⁇ tion edge. This could be a huge advantage, since low linear transmission and impairment of normal color vision are major concerns for potential users of laser protective devices.
  • broadband two-photon absorbing molecules have been prepared from mixtures of compounds, all of which are essentially transparent over much of the visible spectrum, each with different two-photon resonances that span a wide band. Finally, these two-photon absorbing molecules perform very well at high intensities such that good short pulse performance is assured.
  • optical limiting compositions according to the present invention may exist as crystals, mesoscopic phases, polymers, glasses, liquids or gases.
  • the compositions may be used alone or in combination with other crystals, mesoscopic phases, polymers, glasses, liquids or gases.
  • the multi-photon absorber may be inco ⁇ orated, in the form of a concentration gradient profile, into a material, to form a concentration gradient optical limiting material.
  • concentration gradient materials can be made by solvent-assisted in-diffusion of molecules into porous solids or gels, by sequential deposition of layered thin film materials wherein the concentration of the dye in each layer is varied appropriately. This may be accomplished by forming a laminate structure comprised of thin films of free standing polymer containing the multi-photon absorber.
  • gradient materials can be produced by codeposition of the dye with an inert binder material, with the relative rates of deposition of each material being varied with time to as to form a concentration gradient.
  • solutions of 4,4'- bis(dibutylamino)stilbene (BDAS) in acetone were placed in a 1 cm pathlength cell positioned into the focus of an f/5 focusing lens.
  • the transmitted optical energy was collected with a matched f/5 lens and relayed onto a silicon photodiode detector.
  • Optical limiting responses for solutions with two different concentrations (0.01 and 0.134 moles/liter) of the BDAS were obtained and are shown in Figure 18.
  • the sample linear transmission at 605 nm was 96%.
  • the transmission of the sample at an input energy of 170 ⁇ J dropped to about 0.10.
  • the sample pathlength was 1 cm, the effective interaction length was much smaller, ⁇ 100 ⁇ m, due to the fact that the intensity falls off as z" 2 from the focus and the rate of attenuation due to two-photon abso ⁇ tion depends on the square of the intensity.
  • the rate of attenuation due to two-photon abso ⁇ tion falls off from the focus as Z" 4 .
  • the attenuation rate is reduced by a factor of 4 relative to that at the focus.
  • Figure 18 illustrates two-photon optical limiting responses of 0.01 and 0.134 M solutions of 4,4'-bis(dibutylamino)sti ⁇ bene for ⁇ 5-ns, 600 nm pulses.
  • the straight line corresponds to the linear transmission (96%) of the 0.134 M solution.
  • a 1 cm cell was centered on the focus of an -f/5 optical system (effective interaction length ⁇ 100 ⁇ m) and the total transmitted energy was detected.
  • Solutions or materials containing the multi-photon absorbing molecules according to the invention such as 4,4'-bis(dibutylamino)stilbene, exhibit strong nonlinear optical beam spreading such that the transmitted energy emanating from the absorber is defocused and spread over a larger area for strong inputs compared to weaker ones.
  • greater protection from optical damage is obtained for a detector or sensor placed at the final focal plane of the system.
  • Yet further enhancements in the protection afforded by these multi-photon absorbers can be obtained by placement of a suitable aperture stop at an intermediary focal plane, so as to entirely eliminate the transmitted energy that falls outside the pupil of the stop, as a result of nonlinear beam spreading.
  • Figure 19 shows the nonlinear abso ⁇ tion peaks for 4,4'-bis-(di-n- butylamino)stilbene and 4,4'-bis-(diphenylamino)stilbene and the linear transmission of a mixture of these compounds at a total concentration of 0.1 M.
  • the abso ⁇ tion edge for 4,4'-bis-(di-n-butylamino)stilbene has an onset at 500 nm, so that the material is transparent from 500 nm to longer wavelengths throughout the visible spectral range.
  • the two-photon abso ⁇ tion band occurs in a region of high transparency.
  • the two-photon peak at 600 nm is fairly sha ⁇ , but we have shown that simple diphenyl substitution on the amines gives rise to a broader two-photon peak that is shifted to -690 nm, even though the one photon peak is red shifted by only 20 nm.
  • a mixture of these materials would cover well the range from 560 to 730 nm, as demonstrated in Figure 18.
  • Experiments show that such a mixture of 4,4'-bis(dibutylamino)stilbene and 4,4'- bis(diphenylamino)stilbene shows a net two-photon abso ⁇ tivity that is equal to the sum of the two-photon abso ⁇ tivities of the two individual molecules.
  • Figure 19 illustrates linear transmission spectrum (solid line) of a mixture of 4,4'-bis(dibutylamino)stilbene and 4,4'-bis(diphenylamino)stilbene for a total concentration of 0.1M. Also shown are the wavelength dependent two-photon abso ⁇ tivities for each compound: triangles are for the dibutyl derivative and squares are for the diphenyl derivative.
  • a combination of chromophores with alkyl and aryl substituents on the amino groups of diaminostilbenes produces materials with broadband two-photon abso ⁇ tion and high transparency. Additional shorter wavelength two-photon absorbers could be added with no compromise of the linear transmission in order to further extend the two-photon abso ⁇ tion to cover the whole visible spectrum.
  • a 4,4'-bis(diphenylamino) biphenyl or a 4,4'-bis(diphenylamino) fluorene would add a two-photon abso ⁇ tion band at approximately 500 to 550 nm, but would not reduce the linear transmission.
  • a mechanism to enhance the two-photon abso ⁇ tivity at a given wavelength is to synthesize molecules with extended conjugation such that the single-photon abso ⁇ tion edge approaches the fundamental frequency of the laser, without leading to substantially increased linear loss. For example, simply extending the number of bridging double bonds in the stilbene derivatives from one to five double bonds enhances the effective two-photon abso ⁇ tivity by a factor of five.
  • Figure 20 illustrates nonlinear transmission data showing enhanced two- photon abso ⁇ tion in a l-(4-dimethylaminophenyl)-10-(4-dibutylaminophenyl)- deca-l,3,5,7,9-pentane (squares) as compared to the 4,4'-bis-(di-n- butylamino)stilbene (circles). Measurements were performed at 598 nm using 0.0 IM solutions.
  • Another feature of this invention is the ability to systematically control the position of the lowest two-photon abso ⁇ tion band of bis donor-substituted ⁇ - conjugated molecules by increasing the ⁇ -conjugation length of the molecule by, for example, controlling the number of conjugated double bonds between the two donor-substituted aromatic or heteroaromatic end groups.
  • increasing the number of double bonds leads to a considerable shift of the two-photon abso ⁇ tion band to longer wavelengths.
  • Inco ⁇ oration of phenylene-vinylene groups between the end groups has a similar effect.

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Abstract

La présente invention concerne des composés absorbants multiphotoniques hautement efficaces et leurs procédés d'utilisation. Lesdits composés comportent, en général, un pont de liaisons à conjugaison pi reliant des groupes donneurs d'électrons ou des groupes accepteurs d'électrons. Le pont peut être substitué par un groupe donneur d'électrons ou un groupe accepteur d'électrons. La solubilité, la lipophilie, l'absorption maximale et d'autres caractéristiques peuvent être adaptées par la modification des groupes d'électrons donneurs, des groupes d'électrons accepteurs ou de la nature du pont de conjugaison pi. De nombreux procédés photophysiques et photochimiques sont rendus possibles par la transformation de ces composés en des états électroniquement excités par absorption simultanée d'au moins deux photos de radiation.
PCT/US1997/020596 1996-11-12 1997-11-10 Materiaux optiques a absorption de deux photons ou d'ordre superieur et procedes d'utilisation WO1998021521A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2000230132A (ja) * 1998-12-07 2000-08-22 Sony Corp ビス（アミノスチリル）ベンゼン化合物及びその合成中間体、並びにこれらの製造方法
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5034613A (en) * 1989-11-14 1991-07-23 Cornell Research Foundation, Inc. Two-photon laser microscopy
US5523573A (en) * 1994-01-26 1996-06-04 Haenninen; Pekka Method for the excitation of dyes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5034613A (en) * 1989-11-14 1991-07-23 Cornell Research Foundation, Inc. Two-photon laser microscopy
US5523573A (en) * 1994-01-26 1996-06-04 Haenninen; Pekka Method for the excitation of dyes

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EP2468487A1 (fr) 2006-05-18 2012-06-27 3M Innovative Properties Company of 3M Center Structures d'extraction de lumière et guides d'ondes les incorporant
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EP2043096A1 (fr) 2007-09-28 2009-04-01 FUJIFILM Corporation Matériau d'enregistrement d'absorption à deux photons contenant un colorant disposant d'un groupe polymérisable
EP2239629A4 (fr) * 2008-01-30 2012-10-31 Univ Osaka Matériau d'enregistrement optique, procédé d'enregistrement optique, matériau photosensible, procédé de photolithographie, initiateur de photopolymérisation et agent photosensibilisant
EP2239629A1 (fr) * 2008-01-30 2010-10-13 Osaka University Matériau d'enregistrement optique, procédé d'enregistrement optique, matériau photosensible, procédé de photolithographie, initiateur de photopolymérisation et agent photosensibilisant
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US10703710B2 (en) 2013-01-30 2020-07-07 Ecolab Usa Inc. Hydrogen sulfide scavengers
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US10407626B2 (en) 2015-09-08 2019-09-10 Ecolab Usa Inc. Hydrocarbon soluble/dispersible hemiformals as hydrogen sulfide scavengers
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CN105732477A (zh) * 2016-02-25 2016-07-06 浙江工业大学 分子内电荷转移化合物及其合成方法和应用
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US10336950B2 (en) 2016-07-29 2019-07-02 Ecolab Usa Inc. Antifouling and hydrogen sulfide scavenging compositions and methods
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US10538710B2 (en) 2017-07-13 2020-01-21 Ecolab Usa Inc. Hydrogen sulfide scavengers
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