WO2002008230A1 - Chlorines a substitution trans-beta et procedes de fabrication correspondants - Google Patents

Chlorines a substitution trans-beta et procedes de fabrication correspondants Download PDF

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Publication number
WO2002008230A1
WO2002008230A1 PCT/US2001/022986 US0122986W WO0208230A1 WO 2002008230 A1 WO2002008230 A1 WO 2002008230A1 US 0122986 W US0122986 W US 0122986W WO 0208230 A1 WO0208230 A1 WO 0208230A1
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polymer
chlorin
coupled
positions
group
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PCT/US2001/022986
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English (en)
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Jonathan S. Lindsey
Thiagarajan Balasubramanian
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North Carolina State University
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Priority claimed from US09/621,797 external-priority patent/US6420648B1/en
Priority claimed from US09/852,560 external-priority patent/US6559374B2/en
Application filed by North Carolina State University filed Critical North Carolina State University
Priority to AU2001277059A priority Critical patent/AU2001277059A1/en
Publication of WO2002008230A1 publication Critical patent/WO2002008230A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C09B47/00—Porphines; Azaporphines
    • 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
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/209—Light trapping arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/701—Organic molecular electronic devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention concerns solar cells, particularly regenerative solar cells, and light harvesting arrays useful in such solar cells.
  • the right hand side depicts a simplified photoelectrosynthetic cell. This cell produces both electrical power and chemical products. Many of the molecular approaches over the past few decades were designed to operate in the manner shown with the goal of splitting water into hydrogen and oxygen. Shown on the left hand side is a regenerative cell that converts light into electricity with no net chemistry. In the regenerative solar cell shown, the oxidation reactions that take place at the photoanode are reversed at the dark cathode.
  • thick film sensitizers are provided by the so-called organic solar cells (Tang, C. W. and Albrecht, A. C. J. Chem. Phys. 1975, 63, 953-961).
  • a 0.01 to 5 ⁇ m thick film typically comprised of phthalocyanines, perylenes, chlorophylls, porphyrins, or mixtures thereof, is deposited onto an electrode surface and is employed in wet solar cells like those shown, or as solid-state devices where a second metal is deposited on top of the organic film.
  • the organic layer is considered to be a small bandgap semiconductor with either n- or p-type photoconductivity and the proposed light-to-electrical energy conversion mechanisms incorporate excitonic energy transfer among the pigments in the film toward the electrode surface where interfacial electron transfer takes place.
  • the importance of these proposed mechanistic steps is not clear. Increased efficiencies that result from vectorial energy transfer among the pigments have not been convincingly demonstrated.
  • the reported excitonic diffusion lengths are short relative to the penetration depth of the light. Accordingly, most of the light is absorbed in a region where the energy cannot be translated to the semiconductor surface. The excitons are also readily quenched by impurities or incorporated solvent, leading to significant challenges in reproducibility and fabrication.
  • the state-of-the-art organic solar cells are multilayer organic "heterojunction" films or doped organic layers that yield -2% efficiencies under low irradiance, but the efficiency drops markedly as the irradiance approaches that of one sun (Forrest, S. R. et al., J. Appl. Phys. 1989, 183, 307; Schon, J. H. et al, Nature 2000, 403, 408).
  • Another class of molecular-based solar cells are the so-called photogalvanic cells that were the hallmark molecular level solar energy conversion devices of the 1940's -1950's (Albery, W. J. Ace. Chem. Res. 1982, 15, 142).
  • the cells are distinguished from those discussed above in that the excited sensitizer does not undergo interfacial electron transfer.
  • the cells often contain sensitizers embedded in a membrane that allows ion transfer and charge transfer; the membrane physically separates two dark metal electrodes and photogenerated redox equivalents.
  • the geometric arrangement precludes direct excited-state electron transfer from a chromophore to or from the electrodes. Rather, intermolecular charge separation occurs and the reducing and oxidizing equivalents diffuse to electrodes where thermal interfacial electron transfer takes place.
  • a transmembrane Nernst potential can be generated by photodriven electron transfer occurring in the membrane.
  • chemical fuels may be formed as well.
  • the present invention provides, among other things, trans-substituted chlorins and methods of making such trans substituted chlorins.
  • the trans-substituted chlorins may be used, among other things, as building blocks in polymers that may be incorporated into light harvesting arrays and solar cells described herein.
  • a light harvesting array of the present invention is useful, among other things, for the manufacture of solar cells.
  • the light harvesting array comprises: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to the first electrode, each of the light harvesting rods comprising a polymer of Formula I: ⁇ ll ⁇ m+ ⁇ (I) m wherein: m is at least 1, and may be from two, three or four to 20 or more;
  • X 1 is a charge separation group having an excited-state of energy equal to or lower than that of X 2 ;
  • X 2 through X m+1 are chromophores.
  • X 1 preferably comprises a porphyrinic macrocycle, which may be in the form of a double-decker sandwich compound. Further, X 2 through X m+1 also preferably comprise porphyrinic macrocycles.
  • At least one of (e.g., two, three, a plurality of, the majority of or all of) X 1 through X m+1 is/are selected from the group consisting of chlorins, bacteriochlorins, and isobacteriochlorins, and most preferably is a trans-substituted chlorin as described herein.
  • Light-harvesting arrays provide intense absorption of light and deliver the resulting excited state to a designated location within the molecular array.
  • Light-harvesting arrays can be used as components of low-level light detection systems, especially where control is desired over the wavelength of light that is collected.
  • Light-harvesting arrays can be used as input elements in optoelectronic devices, and as an input unit and energy relay system in molecular-based signaling systems.
  • One application of the latter includes use in molecular-based fluorescence sensors.
  • the molecular-based sensor employs a set of probe groups (which bind an analyte) attached to a molecular backbone that undergoes excited-state energy transfer.
  • a particular application of the light-harvesting arrays described herein is in solar cells.
  • a solar cell as described herein typically comprises:
  • a second substrate comprising a second electrode, with the first and second substrate being positioned to form a space therebetween, and with at least one of (i) the first substrate and the first electrode and (ii) the second substrate and the second electrode being transparent;
  • each of the light harvesting rods comprising a polymer of Formula I: ⁇ l ⁇ ⁇ m + l ⁇
  • X 1 is a charge separation group having an excited-state of energy equal to or lower than that of X ;
  • X 2 through X m+1 are chromophores;
  • X 1 is electrically coupled to the first electrode; the solar cell further comprising
  • an electrolyte in the space between the first and second substrates.
  • a mobile charge carrier can optionally be included in the electrolyte.
  • X 1 through X m+1 is/are selected from the group consisting of chlorins, bacteriochlorins, and isobacteriochlorins, and most preferably is a trans-substituted chlorin as described herein.
  • a variety of different electrical devices comprised of a solar cell as described above having circuits (typically resistive loads) electrically coupled thereto can be produced with the solar cells of the invention, as discussed in greater detail below.
  • Figure 1 Diagrams of the two common molecular approaches for light to electrical energy conversion.
  • Figure 4 Pairwise interaction of chlorin building blocks upon incorporation in covalently linked arrays.
  • Figure 5. The highest occupied molecular orbital of a chlorin is an a orbital, which places electron density at each of the meso and non-reduced ⁇ sites.
  • Figure 6 illustrates the synthesis of a trans-chlorin building block with two ⁇ substituents.
  • Figure 7 A The synthesis of the new ⁇ -substituted Eastern half for chlorin synthesis.
  • Figure 7B The synthesis of the new ⁇ -substituted Eastern half for chlorin synthesis, extending the route shown in Figure 34A.
  • Figure 8 illustrates the synthesis of the new ⁇ -substituted Western half for a chlorin building block.
  • Figure 10 illustrates a cataract linear array employing domains comprised of multiple isoenergetic pigments.
  • Figure 11 illustrates reactions suitable for preparing light-harvesting rod oligomers.
  • Figure 13 illustrates the synthesis of meso-substituted chlorins by previously disclosed techniques.
  • Figure 14 illustrates the synthesis of ⁇ -substituted chlorin eastern half (EH) precursors.
  • Figure 15 further illustates the synthesis of ⁇ -substituted chlorin eastern half precursors.
  • Figure 16 illustrates the synthesis of a ⁇ -substituted chlorin western half (WH).
  • Figure 17 illustrates the synthesis of a ⁇ -substituted chlorin.
  • Figure 18 illustrates the synthesis of a trans ⁇ -substituted chlorin.
  • a substrate as used herein is preferably a solid material (which may be flexible or rigid) suitable for the attachment of one or more molecules.
  • Substrates can be formed of materials including, but not limited to glass, organic polymers, plastic, silicon, minerals (e.g. quartz), semiconducting materials, ceramics, metals, etc.
  • the substrate may be in any suitable shape, including flat, planar, curved, rod-shaped, etc.
  • the substrate may be inherently conductive and serve itself as an electrode, or an electrode may be formed on or connected to the substrate by any suitable means (e.g., deposition of a gold layer or a conductive oxide layer).
  • Either or both of the substrates in the solar cells may be transparent (that is, wavelengths of light that excite the chromophores can pass through the substrate and corresponding electrode, even if they are visually opaque).
  • the substrate and electrode may be of any suitable type.
  • One of the substrates may be opaque with respect to the wavelengths of light that excite the chromophores.
  • One of the substrates may be reflective or provided with a reflective coating so that light that passes through the arrays or rods is reflected back to the arrays or rods.
  • electrode refers to any medium capable of transporting charge (e.g. electrons) to and/or from a light harvesting rod.
  • Preferred electrodes are metals (e.g., gold, aluminum), non-metals (e.g., conductive oxides, carbides, sulfide, selinides, tellurides, phosphides, and arsenides such as cadmium sulfide, cadmium telluride, tungsten diselinide, gallium arsenide, gallium phosphide, etc.), and conductive organic molecules.
  • the electrodes can be manufactured to virtually any 2- dimensional or 3 -dimensional shape.
  • conductive oxide refers to any suitable conductive oxide including binary metal oxides such as tin oxide, indium oxide, titanium oxide, copper oxide, and zinc oxide, or ternary metal oxides such as strontium titanate and barium titanate.
  • binary metal oxides such as tin oxide, indium oxide, titanium oxide, copper oxide, and zinc oxide
  • ternary metal oxides such as strontium titanate and barium titanate.
  • suitable conductive oxides include but are not limited to indium tin oxide, titanium dioxide, tin oxide, gallium indium oxide, zinc oxide, and zinc indium oxide.
  • the metal oxide semiconductors may be intrinsic or doped, with trace amounts of materials, to control conductivity.
  • heterocyclic ligand generally refers to any heterocyclic molecule consisting of carbon atoms containing at least one, and preferably a plurality of, hetero atoms (e.g., N, O, S, Se, Te), which hetero atoms may be the same or different, and which molecule is capable of forming a sandwich coordination compound with another heterocyclic ligand (which may be the same or different) and a metal.
  • heterocyclic ligands are typically macrocycles, particularly tetrapyrrole derivatives such as the phthalocyanines, porphyrins, and porphyrazines
  • porphyrinic macrocycle refers to a porphyrin or porphyrin derivative.
  • Such derivatives include porphyrins with extra rings ortho-fused, or ortho- perifused, to the porphyrin nucleus, porphyrins having a replacement of one or more carbon atoms of the porphyrin ring by an atom of another element (skeletal replacement), -derivatives having a replacement of a nitrogen atom of the porphyrin ring by an atom of another element (skeletal replacement of nitrogen), derivatives having substituents other than hydrogen located at the peripheral (meso-, ⁇ -) or core atoms of the porphyrin, derivatives with saturation of one or more bonds of the porphyrin (hydroporphyrins, e.g., chlorins, bacteriochlorins, isobacteriochlorins, decahydroporphyrins, corphins, pyrrocorphins, etc.), derivatives obtained by coordination of one or more
  • porphyrin refers to a cyclic structure typically composed of four pyrrole rings together with four nitrogen atoms and two replaceable hydrogens for which various metal atoms can readily be substituted.
  • a typical porphyrin is hemin.
  • chlorin is essentially the same as a porphyrin, but differs from a porphyrin in having one partially saturated pyrrole ring.
  • the basic chromophore of chlorophyll, the green pigment of plant photosynthesis, is a chlorin.
  • a "bacteriochlorin” is essentially the same as a porphyrin, but differs from a porphyrin in having two partially saturated non-adjacent (i.e., trans) pyrrole rings.
  • isobacteriochlorin is essentially the same as a porphyrin, but differs from a porphyrin in having two partially saturated adjacent (i.e., cis) pyrrole rings.
  • sandwich coordination compound or “sandwich coordination complex” refer to a compound of the formula L 1 ⁇ " "1 , where each L is a heterocyclic ligand such as a porphyrinic macrocycle, each M is a metal, n is 2 or more, most preferably 2 or 3, and each metal is positioned between a pair of ligands and bonded to one or more hetero atom (and typically a plurality of hetero atoms, e.g., 2, 3, 4, 5) in each ligand (depending upon the oxidation state of the metal).
  • sandwich coordination compounds are not organometallic compounds such as ferrocene, in which the metal is bonded to carbon atoms.
  • the ligands in the sandwich coordination compound are generally arranged in a stacked orientation (i.e., are generally cofacially oriented and axially aligned with one another, although they may or may not be rotated about that axis with respect to one another). See, e.g., D. Ng and J. Jiang, Chem. Soc. Rev. 26, 433-442 (1997).
  • Sandwich coordination compounds may be "homoleptic” (wherein all of the ligands L are the same) or "heteroleptic” (wherein at least one ligand L is different from the other ligands therein).
  • double-decker sandwich coordination compound refers to a sandwich coordination compound as described above where n is 2, thus having the formula L'-M ⁇ L 2 , wherein each of L 1 and L 2 may be the same or different. See, e.g., J. Jiang et al. , J. Porphyrins Phthalocyanines 3, 322-328 (1999).
  • multiporphyrin array refers to a discrete number of two or more covalently-linked porphyrinic macrocycles.
  • the multiporphyrin arrays can be linear, cyclic, or branched, but are preferably linear herein.
  • Light harvesting rods herein are preferably multiporphyrin arrays.
  • the light harvesting rods or multiporphyrin arrays may be linear (that is, all porphyrinic macrocycles may be linked in trans) or may contain one or more bends or "kinks" (for example, by including one or more nonlinear linkers in a light-harvesting rod, or by including one or more cw-substituted porphyrinic macrocycles in the light harvesting rod)
  • Some of the porphyrinic macrocycles may further include additional ligands, particularly porphyrinic macrocycles, to form sandwich coordination compounds as described further below.
  • the rods optionally but preferably are oriented substantially perpendicularly to either, and most preferably both, of the first and second electrodes.
  • Chrophore means a light-absorbing unit which can be a unit within a molecule or can comprise the entire molecule.
  • a chromophore is a conjugated system (alternating double and single bonds which can include non- bonded electrons but is not restricted to alternating double and single bonds since triple and single bonds, since mixtures of alternating triple/double and single bonds also constitute chromophores.
  • Heteroatoms can be included in a chromophore.).
  • chromophores examples include the cyclic 18 pi-electron conjugated system that imparts color to porphyrinic pigments, the linear system of alternating double and single bonds in the visual pigment retinal, or the carbonyl group in acetone.
  • Charge separation group and charge separation unit refer to molecular entities that upon excitation (by direct absorption or energy transfer from another absorber) displace an electron to another part of the same molecule, or transfer an electron to a different molecule, semiconductor, or metal.
  • the “charge separation group” and “charge separation unit” results in storage of some fraction of the excited state energy upon displacement or transfer of an electron.
  • the “charge separation group” and “charge separation unit” is located at the terminus of a light- harvesting array or rod, from which excited-state energy is received.
  • the “charge separation group” and “charge separation unit” facilitates or causes conversion of the excited-state energy into a separate electron and hole or an electron-hole pair.
  • the electron can be injected into the semiconductor by the "charge separation group” or “charge separation unit”. It is feasible that the “charge separation group” and “charge separation unit” could extract an electron from a different molecule or semiconductor, thereby creating a negative charge on the "charge separation group” and “charge separation unit” and a hole in the other molecule or semiconductor.
  • the reaction center of bacterial photosynthesis is a premier example of a “charge separation group” or “charge separation unit”.
  • Synthetic porphyrin-quinone or porphyrin-buckyball molecules also function to absorb light and utilize the resulting energy to separate charge.
  • substituted as used in the formulas herein, particularly designated by S or S" where n is an integer, in a preferred embodiment refer to electron-rich or electron-deficient groups (subunits) that can be used to adjust the redox potential(s) of the subject compound.
  • Preferred substituents include, but are not limited to, H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl.
  • a substituted aryl group is attached to a porphyrin or a porphyrinic macrocycle, and the substituents on the aryl group are selected from the group consisting of aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl.
  • substituents include, but are not limited to, 4-chlorophenyl, 4- trifluoromethylphenyl, and 4-methoxyphenyl.
  • Preferred substituents provide a redox potential range of less than about 5 volts, preferably less than about 2 volts, more preferably less than about 1 volt.
  • aryl refers to a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc. (i.e., either the 6-carbon ring of benzene or the condensed 6-carbon rings of the other aromatic derivatives).
  • an aryl group may be phenyl (C 6 H 5 ) or naphthyl (C 10 H 7 ). It is recognized that the aryl group, while acting as substituent can itself have additional substituents (e.g. the substituents provided for S n in the various formulas herein).
  • alkyl refers to a paraffinic hydrocarbon group, typically Cl to C4, which may be derived from an alkane by dropping one hydrogen from the formula. Examples are methyl (CH 3 -), ethyl (C H 5 -), propyl (CH 3 CH CH -), isopropyl ((CH 3 ) 2 CH-).
  • alkenyl refers to a hydrocarbon group, typically C2 to C4, derived from the corresponding alkyl and which contains at least one double bond (e.g., butadienyl).
  • alkynyl refers to a hydrocarbon group, typically C2 to C4, derived from the corresponding alkyl and which contains at least one triple bond (e.g., butadiynyl).
  • halogen refers to one of the electronegative elements of group VII A of the periodic table (fluorine, chlorine, bromine, iodine, astatine).
  • perfluoroalkyl refers to an alkyl group where every hydrogen atom is replaced with a fluorine atom.
  • perfluoroaryl refers to an aryl group where every hydrogen atom is replaced with a fluorine atom.
  • pyridyl refers to an aryl group where one CR unit is replaced with a nitrogen atom.
  • sulfoxyl refers to a group of composition RS(O)- where R is some alkyl, aryl, cycloalkyl, perfluoroalkyl, or perfluoroaryl group. Examples include, but are not limited to methylsulfoxyl, phenylsulfoxyl, etc.
  • sulfonyl refers to a group of composition RSO 2 - where R is some alkyl, aryl, cycloalkyl, perfluoroalkyl, or perfluoroaryl group. Examples include, but are not limited to methylsulfonyl, phenylsulfonyl, jp-toluenesulfonyl, etc.
  • R 1 and R 2 are H or some alkyl, aryl, cycloalkyl, perfluoroalkyl, or perfluoroaryl group. Examples include, but are not limited to N-ethylcarbamoyl, N,N- dimethylcarbamoyl, etc.
  • amido refers to the group of composition R ! CO ⁇ (R 2 )- where R 1 and R 2 are H or some alkyl, aryl, cycloalkyl, perfluoroalkyl, or perfluoroaryl group.
  • acyl refers to an organic acid group in which the -OH of the carboxyl group is replaced by some other substituent (RCO-). Examples include, but are not limited to acetyl, benzoyl, etc.
  • a linker is a molecule used to couple two different molecules, two subunits of a molecule, or a molecule to a substrate. When all are covalently linked, they form units of a single molecule.
  • electrically coupled when used with reference to a light harvesting rod and electrode, or to chromophores, charge separation groups and electrodes, refers to an association between that group or molecule and the coupled group or electrode such that electrons move from the storage medium/molecule to the electrode or from the electrode to the molecule and thereby alter the oxidation state of the storage molecule.
  • Electrical coupling can include direct covalent linkage between the storage medium/molecule and the electrode, indirect covalent coupling (e.g. via a linker), direct or indirect ionic bonding between the storage medium/molecule and the electrode, or other bonding (e.g. hydrophobic bonding).
  • no actual bonding may be required and the light, harvesting rod may simply be contacted with the electrode surface. There also need not necessarily be any contact between the electrode and the light harvesting rod where the electrode is sufficiently close to the light harvesting rod to permit electron tunneling between the medium/molecule and the electrode.
  • Excited-state energy refers to the energy stored in the chromophore in a metastable state following absorption of light (or transfer of energy from an absorber).
  • the magnitude of the "excited-state energy” is estimated by energy of the shortest wavelength fluorescence (phosphorescence) band.
  • the magnitude of the "excited-state energy” is greater than or equal to the energy of the separated electron and hole following charge separation.
  • Electrolytes used to carry out the present invention may be aqueous or non- aqueous electrolytes, including polymer electrolytes.
  • the electrolyte may comprise or consist of a solid, in which latter case the solar cell can be produced devoid of liquid in the space between the first and second substrates.
  • the electrolyte consists of or comprises a substance that increases the electrical conductivity of a carrier medium.
  • Most electrolytes are salts or ionic compounds. Examples include sodium chloride (table salt), lithium iodide, or potassium bromide in water; tetrabutylammonium hexafluorophosphate or tetraethylammonium perchlorate in acetonitrile or dichloromethane; or an ionic polymer in a gel.
  • Mobile charge carriers refers to an ion, molecule, or other species capable of translating charges (electrons or holes) between the two electrodes in a solar cell. Examples include quinones in water, molten salts, and iodide in a polymer gel such as polyacrylonitrile. Examples of mobile charge carriers include, but are not limited to, iodide, bromide, tetramethyl-l,4-phenylenediamine, tetraphenyl-1,4- phenylenediamine, ⁇ »-benzoquinone, C 60 , C 70 , pentacene, tetrathiafulvalene, and methyl viologen.
  • chlorin building blocks designed to give efficient energy transfer in chlorin-containing light-harvesting arrays are presented. Objectives are to (1) prepare chlorins with two functional handles such that the chlorins can be readily incorporated into linear arrays, (2) design the chlorin building blocks to have the highest possible value of the orientation term for TS energy transfer, and (3) be connected appropriately to give the most extensive TB energy transfer process.
  • Four possible trans-substituted chlorins are displayed in Figure 2. Two ⁇ , ⁇ '-substituted chlorins are shown, as are two chlorins each bearing two meso substituents.
  • chlorin building blocks I and II are slightly preferred over III and IV for TS energy transfer.
  • the trans configuration can be achieved with connection to rings A and C. Comparing the four possible trans-chlorins shown in Scheme 4 for TB energy transfer, it is seen that the meso-substituted chlorins (III, IV) are inferior to the ⁇ , ⁇ '-substituted chlorins (I, II).
  • Chlorins with substituents in a trans orientation are highly desirable for elaboration into linear light-harvesting rods.
  • Such chlorins include those with substitution at the 2 and 12-positions, the 3 and 13 -positions, or the 5 and 15- positions.
  • the starting material for the synthesis of 2,12-substituted chlorins is a 2-formyl-3-aryl pyrrole. The synthesis of the latter involves formylation of a 3 -aryl pyrrole.
  • a tr ⁇ '-substituted chlorin of the present invention comprises compounds of Formula X:
  • M is a metal, such as a metal selected from the group consisting of Zn, Mg, Pt, Pd, Sn and Al, or M is absent (in which case the ring hetero atoms K 1 through K 4 are substituted with H,H as required to satisfy neutral valency);
  • K 1 , K 2 , K 3' , and K 4 are hetero atoms, such as hetero atoms independently selected from the group consisting of N, O, S, Se, Te, and CH.
  • K is N.
  • S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , and S 14 are independently selected substituents (that may optionally provide a redox potential of less than about 5, 2 or even 1 volt).
  • n is from 0 or 1 to 5 or 10;
  • R may be present or absent (in one embodiment when n is 0 then R is present; in another embodiment, when n is 0 R 3 may also be absent);
  • R 1 , R 2 , and R 3 are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups (e.g., phenyl, and derivatives of pyridine, thiophene, pyrrole, phenyl, etc.), which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl.
  • heteroaryl groups e.g., phenyl, and derivatives of pyridine, thiophene, pyrrole
  • Y may be a protected or unprotected reactive site or group on the linker such as a hydroxy, thio, seleno, telluro, carboxy, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo (e.g., iodo, bromo, chloro), alkenyl, alkynyl, haloalkyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups.
  • halo e.g., iodo, bromo, chloro
  • tr ⁇ r ⁇ -substituted chlorins as described above are made by: (a) condensing a compound of formula WH with a compound of formula EH in an organic solvent in the presence of an acid to form a condensation product;
  • Z is halo (e.g., Br, Cl, I), alkoxy, or acetoxy
  • the condensing step is carried out under acidic conditions (e.g., 1 or 10 to 20 or 200 mM, depending upon the acid) in an organic solvent.
  • the organic solvent is typically a polar or nonpolar, protic or aprotic solvent such as methylene chloride, acetonitrile, or toluene.
  • a Bronsted or Lewis acid is included in the solvent, such as trifluoroacetic acid or BF 3 -etherate.
  • the condensing step may be carried out at any suitable temperature and pressure, such as 0° to 25°C and ambient pressure.
  • the oxidative cyclization step is carried out in a polor or nonpolar, protic or aprotic organic solvent as described above, in the presence of a metal salt MX or MX 3 , where X is an anion such as acetate, chloride, iodide, etc.
  • a metal salt MX or MX 3 where X is an anion such as acetate, chloride, iodide, etc.
  • Any suitable base may be employed, with piperidine currently preferred.
  • Any suitable oxidant may be employed, with silver iodate or oxygen currently preferred.
  • the reaction may be carried out at any suitable temperature and pressure, such as 25° to 100°C and ambient pressure.
  • metal M may optionally be removed to form the free base chlorin simply by displacing with an acid (e.g., acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, etc.) in accordance with standard techniques.
  • an acid e.g., acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, etc.
  • a wide variety of metals can be employed, given that the metals meet the requirement of affording a photochemically active excited state.
  • Preferred embodiments of such metals are Zn, Mg, Pd, Sn, and Al.
  • the chlorin-forming reaction yields the zinc chlorin, which is easily demetalated with mild acid to give the free base chlorin.
  • the desired metallochlorin can then be prepared via well known metalation reactions.
  • this array employing multiple isoenergetic pigments (one or more of which may be chlorins of the present invention), is illustrated in Figure 10.
  • Such arrays may be produced in accordance with known techniques and the techniques disclosed below.
  • Oxochlorins may be considered as a particular type of chlorin. Oxochlorins and chlorins have similar spectral properties but the oxochlorins are more resistant to oxidation than are chlorins. In fact, oxochlorins have oxidation potentials similar to those of porphyrins whereas chlorins have lower oxidation potentials than porphyrins. Thus, broadly speaking, an oxochlorin has the spectral properties of a chlorin and the oxidation properties of a porphyrin.
  • the time-honored method for forming oxochlorins employs treatment of a ⁇ - substituted porphyrin with OsO 4 forming the vicinal diol, which upon acid-catalyzed pinacol rearrangement yields the oxochlorin bearing a geminal dialkyl group (Chang, C. K.; Sotiriou, C. J. Heterocyclic Chem. 1985, 22:1739-1741).
  • application of this approach to porphyrin building blocks bearing specific patterns of substituents at the perimeter of the macrocycle typically results in a mixture of oxochlorins (Osuka, A., et al, J. Am. Chem. Soc. 1996, 118: 155-168).
  • a polymer of the present invention comprises a plurality of monomers, each of said monomers comprising a porphyrinic macrocycle, wherein at least one (e.g., two, three or all) of said porphyrinic macrocycles is an independently selected chlorin, and wherein each of said chlorins is: (i) coupled to one or two adjacent porphyrinic macrocycles in said polymer at the 2 position, the 12 position, or both the 2 and 12 positions (when the monomer is internal); or (ii) coupled to one or two adjacent porphyrinic macrocycles in said polymer at the 3 position, the 13 position, or both the 3 and 13 positions (when the monomer is internal).
  • the monomers in the polymer may be directly linked to one another via a covalent bond or linked via linking groups, depending upon the monomer used and the synthetic reaction employed.
  • the polymer may be of any size, but typically consists of from 2 or 3 to 50, 100 or 200 porphyrinic macrocycle monomers.
  • the polymer may be bound to a conductive substrate to form an electrode, which electrode may be used in the light harvesting arrays and solar cells described herein.
  • the synthesis of the oligomers can be performed using stepwise methods or using polymerization methods. Both methods generally require two reactive groups attached to the pigment building block in order to prepare a polymer where the pigment building blocks are integral components of the polymer backbone. (An alternative, less attractive design yields pendant polymers where the pigment building blocks are attached via one linkage to the polymer backbone.)
  • the stepwise synthetic method generally requires the use of protecting groups to mask one reactive site, and one cycle of reactions then involves coupling followed by deprotection. In the polymerization method no protecting groups are employed and the polymer is prepared in a one-flask process. The polymerizations can take place in solution or can be performed with the polymer growing from a surface.
  • the polymerization can be performed beginning with a solid support as in solid-phase peptide or DNA synthesis, then removed, purified, and elaborated further for specific applications.
  • the polymerization with the nascent polymer attached to an electroactive surface generates the desired light- harvesting material in situ. This latter approach is exceptionally attractive in eliminating the need for handling of the polymers.
  • the ability to avoid handling of the polymers makes possible the synthesis of compounds that do not exhibit sufficient solubility in most solvents for convenient handling (dissolution, purification, processing, solution characterization).
  • Polymers can be created that are composed of identical units, or dissimilar units as in block copolymers or random copolymers.
  • the polymerization can be performed to create a linear array where the composition of different pigment building blocks is organized in a gradient. This latter approach affords the possibility of creating an energy cascade for the flow of excited-state energy and/or the reverse flow of ground-state holes in a systematic manner along the length of the array.
  • a polymerizable unit (pigment building block or linker) is attached to the surface (for Au, a thiol attacliment group is used for Y 1 ; for TiO 2 , a carboxylic acid attachment group is used for Y 2 ).
  • the first pigment building block (BB ) is added and the coupling reagents are added in order to perform the polymerization (e.g., a Glaser coupling). Then the surface is washed to remove the coupling reagents (copper reagents in the case of the Glaser coupling) and any
  • a thiol attachment group (X) is used, creating the self-assembled monolayer on gold.
  • Such self-assembled monolayers are known for thiol-derivatized porphyrins (Gryko, D. T. et al., J Org. Chem. 1999, 64, 8635-8647).
  • a carboxylic acid attachment group is used for the attachment (Y).
  • the polymerizable groups can be any of the type described above using the various name reactions (Glaser, Sonogashira, Cadiot-Chodkiewicz, Heck, Wittig, Suzuki, etc.).
  • the final polymeric product is comprised of domains of the various pigment building blocks [(BB') n ] in a linear array.
  • Chlorin monomers and chlorin-containing polymers of the present invention are useful for the production of light harvesting arrays and solar cells as described above, and as active agents for photodynamic therapy.
  • Solar cells of the present invention can be used in a variety of different electrical devices. Such devices typically comprise a solar cell as described above, and a circuit (e.g., a resistive load) electrically coupled to said solar cell (e.g., by providing a first electrical coupling of the circuit to one electrode of the solar cell, and a second electrical coupling of the circuit to the other electrode of the solar cell).
  • the solar cell may provide the sole source of power to the circuit, may be a supplemental source, may be incorporated to charge a battery, etc.
  • any of a variety of different electrical devices may incorporate a solar cell of the invention, including but not limited to radios, televisions, computers (such as personal computers), processors, calculators, telephones, wireless communication devices such as pagers, watches, emergency location devices, electric vehicles, emergency power supplies, power generators, lights or lamps, and other illuminating devices, monitoring devices, inspection devices, radiation detectors, imaging devices, optical coupling devices.
  • the major isomer was the desired compound (5) and was obtained in pure form by recrystallization in 62% yield. Protection of the pyrrolic nitrogen with the BOC group (Tietze, L. F.; Kettschau, G.; Heitmann, K. Synthesis 1996, 851-857) gave pyrrole 6 in quantitative yield. Reduction to alcohol 7 was achieved by treatment with LiBH at low temperature (longer reaction time or higher temperature led to the over-reduced and deprotected compound 2-methyl-3-(4-iodophenyl)pyrrole). Treatment of 7 with excess pyrrole under acidic conditions furnished the ⁇ -substituted, mono-protected dipyrromethane 8 in 68% yield.
  • a second ⁇ -substituted dipyrromethane was prepared by Sonogashira coupling (Sonogashira, K. et al., Tetrahedron Lett. 1975, 4467-4470) of iodophenyl-substituted 10 with trimethylsilylacetylene. In this manner the trimethylsilylethynyl dipyrromethane 12 was obtained in quantitative yield (Figure 15). Reaction of 12 with NBS at -78 °C furnished the corresponding bromodipyrromethane 13 in 91% yield.
  • Chlorin Formation Prior synthesis of chlorins involved (1) formation of the bromodipyrromethane-monocarbinol (2-OH, EH) by reduction of the carbonyl group in the EH precursor, (2) acid-catalyzed condensation of the EH and WH (1) to obtain the dihydrobilene- ⁇ , and (3) oxidative metal-mediated cyclization to give the chlorin (Strachan, J. P.; O'Shea, D. F.; Balasubramanian, T.; Lindsey, J. S. J. Org. Chem. 2000, 65, 3160-3172). All the three steps are done in succession on the same day.
  • the chlorins Zn22-24 each bear one ⁇ substituent.
  • 13-OH and Western half 21 were reacted to give zinc chlorin Zn-25 in 24% yield ( Figure 18).
  • This chlorin has an iodophenyl group and an ethynylphenyl group at ⁇ positions on opposite sides of the macrocycle.
  • Porphyrins bearing iodophenyl and ethynylphenyl groups in a trans orientation have been employed in the stepwise synthesis of linear multi-porphyrin arrays (Wagner, R. W.; Lindsey, J. S. J. Am. Chem. Soc.
  • the Zn-chlorins were demetalated to give the corresponding free base chlorins by treatment with TFA in CH 2 C1 2 .
  • the crude product was pure enough for analysis while in other cases the free base chlorin was further purified by a short silica column.
  • the reduced ring exhibits a singlet at ⁇ 2.07 ppm (geminal dimethyl groups) and another singlet at ⁇ 4.64 ppm (ring CH ), as also observed in the meso-substituted chlorins.
  • Other characteristic features include an AB quartet at ⁇ 8.85 ppm ( ⁇ -pyrrole protons of ring A), two doublets at ⁇ 8.64 and 8.90 ppm ( ⁇ -pyrrole protons of ring B), and singlets at ⁇ 8.91 (for 2H) and 8.99 ppm (two meso protons at C-15 and C-20, and one ⁇ -pyrrole proton of ring C).
  • Characteristic features in addition to the different chemical shifts of the two NH protons include the singlet at ⁇ 8.64 ppm ( ⁇ -pyrrole proton of ring B) and the downfield signal at ⁇ 9.17 ppm as a doublet (one of the ⁇ -pyrrole protons of ring C).
  • the ! H NMR spectrum of chlorin 25 is more simple.
  • the ⁇ -pyrrole protons of ring B appear as two doublets at ⁇ 8.62 and 8.88, and the AB quartet corresponding to the ⁇ -pyrrole protons of ring A in chlorins 22-24 is absent.
  • the remaining meso protons and ⁇ -pyrrole protons resonate as five singlets.
  • Zn-25 showed a similar pattern except for the slight upfield shift of the peaks due to the meso and ⁇ protons.
  • a distinctive feature of this set of chlorins is that the ⁇ -pyrrole protons of ring B appear slightly upfield compared to the other pyrrole protons. This indicates that the ⁇ -pyrrole double bond of ring B does not participate as fully in the 18 ⁇ electron ring current of the chlorin macrocycle.
  • Absorption Spectra Each of the free base chlorins (22-25) exhibits an intense Soret band and a characteristic strong Q y band. The Soret band in each case exhibited a short-wavelength shoulder of significant intensity, resulting in a fwhm ranging from 32-35 nm for 22-25. A similar spectral feature was observed for the, previous set of meso-substituted free base chlorins that were examined.
  • the Soret band red-shifted slightly as the substituent was moved from position 8 (24) to 12 (22, 23) to 2 and 12 (25).
  • Significant differences in Q y absorption maximum and absorption intensity occurred depending on the site of substitution of the chlorin.
  • the Q y absorption maximum ranged from 637 to 655 nm, and paralleled the redshift of the Soret band.
  • a hyperchromic effect of the Q y band was observed accompanying the bathochromic shift.
  • the ratio of the Q y and Soret bands provides a relative measure of the changing band intensities.
  • the Soret/Q y band ratio decreases from 4.3 (24) to 2.5 (25).
  • chlorins with an iodophenyl or ethynylphenyl group at the 12 position exhibited nearly identical absorption spectra.
  • meso-substituted free base chlorins exhibited absorption maxima at 411-414 nm and 640-644 nm.
  • Each of the zinc chlorins (Zn-22 - Zn25) exhibits an intense Soret band and a characteristic strong Q y band.
  • the Soret band in each case was sharp (fwhm 18-21 nm) with only a very weak short-wavelength shoulder.
  • the Q y band underwent a redshift from 606 nm to 628 nm as the substituent location was changed from 8 (Zn- 24) to 12 (Zn-22, Zn-23) to 2 and 12 (Zn-25).
  • a concomitant increase in intensity of the Q y band also was observed.
  • the former has the shortest wavelength Q y band (606 nm) but a Soret band at 415 nm, compared with 615 nm and 411 nm for that of the latter.
  • the meso-substituted zinc chlorins exhibited absorption maxima at 412 nm and 608 nm.
  • the free base chlorins 22-24 exhibit a characteristic sharp fluorescence band at 640 nm and a weaker emission in the region 660 - 720 nm. The latter exhibited two discernible maxima at approximately 680 and 710 nm.
  • the emission spectrum of free base chlorin 25 was shifted to 660 nm and 726 nm.
  • the Zn chlorins Zn-22 and Zn-23 each exhibit a sharp fluorescence band at around 620 nm and a weak band at 676 nm, whereas the emission of Zn-24 appears at 609 and 661 nm.
  • the emission spectrum of Zn-25 is more red shifted as observed in free base 25 (635 and 691 nm).
  • the fluorescence quantum yields were determined for those chlorins lacking iodophenyl substituents (which exhibit decreased yields due to the heavy atom effect).
  • the fluorescence quantum yield of free base chlorin 23 was 0.25, while that of Zn-23 was 0.11. These values are in line with those of other naturally occurring or synthetic chlorins.
  • the synthesis of chlorins described herein provides the following features: (1) control over the location of the reduced ring, (2) locking in of the chlorin hydrogenation level through use of a geminal dimethyl group, (3) location of synthetic handles at designated sites at the perimeter of the macrocycle, and (4) a single chlorin product thereby facilitating purification.
  • the ability to incorporate substituents at distinct locations (2, 5, 8, 10, or 12) about the chlorin perimeter opens a number of opportunities. With different substitution patterns, the Q y absorption band can be tuned over the range 637-655 nm for free base chlorins and 606-628 nm for zinc chlorins, enabling greater spectral coverage.
  • the chlorin bearing synthetic handles at the 2 and 12 positions (25) should enable the incorporation of chlorin building blocks into linear architectures.
  • the availability of a family of synthetic chlorins bearing diverse substituents at defined locations should facilitate the systematic study of substituent effects and broaden the scope of chlorin containing model systems.
  • the two regioisomers formed were purified by two successive flash columns [silica, hexanes/ethyl acetate (3:1)], affording the minor isomer 16 (130 mg, 25%) and the major isomer 10 (270 mg, 53%).
  • reaction was monitored by TLC and after stirring for 2 h, the TLC showed the appearance of a new component and the disappearance of 5. (A longer reaction time (10 h) led to formation of the Michael addition product, 2-(l,3-dinitro-2-propyl)-3-(4- iodophenyl)pyrrole, in -30% yield.) The reaction was quenched with brine, extracted with ethyl acetate, and the organic layers were dried (Na 2 SO 4 ) and concentrated.
  • the nitronate anion of 20 formed in the first flask was transferred via a cannula to the buffered TiCl 3 solution in the second flask. Additional THF (3 mL) was added to the nitronate anion flask and the supernatant was also transferred to the buffered TiCl 3 solution. The resulting mixture was stirred at room temperature for 6 h under argon. Then the mixture was extracted with ethyl acetate and the combined organic layers were washed with satd aq NaHCO 3 , water, brine, and then dried (MgSO ). The solvent was removed under reduced pressure at room temperature.
  • the WH 1 (45 mg, 0.24 mmol) was dissolved in a few mL of anhydrous CH 3 CN and combined with 11-OH, then additional anhydrous CH 3 CN was added to give a total of 22 mL CH 3 CN.
  • the solution was stirred at room temperature under argon and TFA (20 ⁇ L, 0.26 mmol) was added.
  • TFA 20 ⁇ L, 0.26 mmol
  • the reaction was monitored by TLC [alumina, hexanes/ethyl acetate (3:1)], which after 25-30 min showed the disappearance of the EH and the appearance of a bright spot just below the WH.
  • the reaction mixture was quenched with 10% aq NaHCO 3 and extracted with distilled CH2CI2 (3 x 25 mL).
  • the color change of the reaction mixture from red to green indicates the formation of chlorin.
  • the reaction mixture was cooled to room temperature then passed through a short column (silica, CH 2 C1 2 ). The major fraction was concentrated and again chromatographed [silica, hexanes/CH 2 Cl 2 (2:1 then 1:1)]. The greenish blue solid obtained was dissolved in a minimum of CH 2 C1 2 and precipitated by adding hexanes, affording a greenish blue solid (25 mg, 18%).

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Abstract

L'invention concerne des chlorines à substitution trans-bêta et des procédés permettant de les fabriquer, ainsi que des polymères formés à partir de ces chlorines ou contenant ces chlorines comme unité(s) monomère(s). L'invention concerne également des bacilles collecteurs de lumière formés à partir des polymères susmentionnés, ainsi que des électrodes transportant ces polymères.
PCT/US2001/022986 2000-07-21 2001-07-20 Chlorines a substitution trans-beta et procedes de fabrication correspondants WO2002008230A1 (fr)

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WO2008038047A2 (fr) * 2006-09-26 2008-04-03 Cryscade Solar Limited Composé organique, couche photovoltaïque et dispositif photovoltaïque organique associé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6916982B2 (en) 2000-07-21 2005-07-12 North Carolina State University Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays
WO2008038047A2 (fr) * 2006-09-26 2008-04-03 Cryscade Solar Limited Composé organique, couche photovoltaïque et dispositif photovoltaïque organique associé
WO2008038047A3 (fr) * 2006-09-26 2008-12-24 Cryscade Solar Ltd Composé organique, couche photovoltaïque et dispositif photovoltaïque organique associé

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