EP2880018A1 - Borhaltige perylenmonoimide, verfahren zu deren herstellung, deren verwendung als bausteine zur herstellung von perylenmonoimidderivaten, monoimidderivate und deren verwendung bei farbstoffsensibilisierten solarzellen - Google Patents

Borhaltige perylenmonoimide, verfahren zu deren herstellung, deren verwendung als bausteine zur herstellung von perylenmonoimidderivaten, monoimidderivate und deren verwendung bei farbstoffsensibilisierten solarzellen

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Publication number
EP2880018A1
EP2880018A1 EP13828249.6A EP13828249A EP2880018A1 EP 2880018 A1 EP2880018 A1 EP 2880018A1 EP 13828249 A EP13828249 A EP 13828249A EP 2880018 A1 EP2880018 A1 EP 2880018A1
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EP
European Patent Office
Prior art keywords
general formula
compounds
alkyl
hydrogen
variables
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13828249.6A
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English (en)
French (fr)
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EP2880018A4 (de
Inventor
Henrike WONNEBERGER
Ingmar Bruder
Robert SEND
Glauco BATTAGLIARIN
Chen Li
Klaus MÜLLEN
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BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Priority to EP13828249.6A priority Critical patent/EP2880018A4/de
Publication of EP2880018A1 publication Critical patent/EP2880018A1/de
Publication of EP2880018A4 publication Critical patent/EP2880018A4/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/70—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with ring systems containing two or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • 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
    • C09B13/00—Oxyketone dyes
    • C09B13/04—Oxyketone dyes of the pyrene series
    • 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
    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
    • C09B3/50—Dibenzopyrenequinones
    • 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
    • H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P80/00—Climate change mitigation technologies for sector-wide applications
    • Y02P80/20—Climate change mitigation technologies for sector-wide applications using renewable energy

Definitions

  • the present invention relates to compounds of general formula I
  • E 2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E 1 ,
  • W a bridging C2 or C3 moiety which may be substituted by one or more alkyl
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy,
  • Y oxygen or NR 12 and hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
  • A is -COOM, -SO3M or -PO3M
  • M hydrogen, alkali metal cation or [NR ' ] 4+ , hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Lg leaving group m 0 or 1 , where in the case of m equal 1 the one Lg is bound either to the 8 or 9
  • R 1 , R 2 independently of each other a moiety of formula Ilia
  • the direct conversion of solar energy to electrical energy in solar cells is based on the internal photoeffect of a semiconductor material, i.e. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact.
  • the photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power.
  • Thin layers or films of metal oxides are known to constitute inexpensive solid semiconductor materials (n-semiconductors), but their absorption, owing to large band gaps, is typically not within the visible region of the electromagnetic spectrum.
  • the metal oxides therefore have to be combined with a photosensitizer which absorbs in the wavelength range of sunlight, i.e. at from 300 to 2000 nm, and, in the electronically excited state, injects electrons into the conduction band of the semiconductor. With the aid of a redox system which is used additionally in the cell and is reduced at the counterelectrode, electrons are recycled to the sensitizer which is thus regenerated.
  • DSCs Dye-sensitized solar cells which are based on titanium dioxide as the semiconductor material are described, for example, in US-A-4 927 721 , Nature 353, p. 737-740 (1991 ) and US- A-5 350 644, and also Nature 395, p. 583-585 (1998) and EP-A-1 176 646.
  • These solar cells comprise monomolecular films of transition metal complexes, especially ruthenium complexes, which are bonded to the titanium dioxide layer via acid groups, as sensitizers and iodine/iodide redox systems present in dissolved form or amorphous organic p-conductors based on spirobifluorenes.
  • metal-free organic dyes have attracted increasing attention as they do not contain any toxic or costly metal and their properties are easily tuned by facile structural modification.
  • they generally have much higher extinction coefficients when compared to Ru(ll) polypyridyls, making them excellent for use in solid state DSCs in combination with hole transporting materials such as P3HT as shown, for example, by G. K. Mor, S. Kim, M. Paulose, O. K. Varghese, K. Shankar, J. Basham and C. A. Grimes, Nano Lett., 2009, 9, 4250, or spiro-MeOTAD as shown, for example, by H. J. Snaith, A. J. Moule, C. Klein, K. Meerholz, R. H. Friend, M. Gratzel, Nano Lett., 2007, 7, 3372.
  • T. Teraoka, S. Hiroto and H. Shinokubo (Org. Lett. 201 1 , Vol. 13, No. 10, 2532-2535) and G. Battagliarin, C. Li, V. Enkelmann and K. Mullen (Org. Lett. 201 1 , Vol. 13, No. 12, 3012-3015) describe the preparation of the 2,5,8,1 1-tetraboronic ester erylenediimides
  • E 2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E 1 ,
  • W a bridging C2 or C3 moiety which may be substituted by one or more alkyl
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy,
  • R 12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein is -COOM, -SO3M or -PO3M, M hydrogen, alkali metal cation or [NR ' ] 4+ ,
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • Preferred compounds of general formula I are those wherein the variables have the following meaning
  • E , E 2 a moiety selected from the group consisting of
  • E , E 2 a moiety selected from the group consisting of
  • E 2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E 1 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy,
  • R 12 alkyl, or a moiety of formula -Z-A, wherein
  • A is -COOM
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different and
  • Z is Ci-C6-alkylene or 1 ,4-phenylene.
  • a further objective of the instant invention is a process for the preparation of compounds of general formula I which comprises reacting a compound of general formula I*
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4
  • R12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SO3M or -PO3M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • a preferred process for the preparation of compounds of general formula I according to the instant invention comprises reacting a compound of general for
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy,
  • R 12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SOsM or -P0 3 M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • a specifically preferred process for the preparation of compounds of general formula I according to the instant invention comprises reacting a compound of general for
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy,
  • R 12 alkyl, or a moiety of formula -Z-A, wherein
  • A is -COOM
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different and
  • Z is Ci-C6-alkylene or 1 ,4-phenylene.
  • ambient pressure denotes basically unconfined reaction conditions, however, not excluding the application of protective gas atmosphere in order to avoid adverse effects by oxygen/air and/or moisture.
  • Inert solvent means a solvent which does not contain moieties with either basic or acidic properties. Especially groups with acidic hydrogen atoms must not be present. In the case of a aromatic or heteroaromatic solvent this may only contain less than three neighboring hydrogen atoms directly bound to the carbon atoms or heteroatoms of the aromatic or heteroaromatic solvent skeleton in order to prevent the aromatic or heteroaromtic solvent from reacting with the boron containing educt.
  • inert solvent is meant to embrace mixtures of inert solvents as well.
  • Suitable inert solvents are e.g. dimethyl formamide (DMF), tetrahydofuran (THF), 1 ,4-dioxan, octane, hexane, pentane, mesitylene, pinacolone etc. and mixtures thereof.
  • a further objective of the instant invention is to provide a process for the preparation of compounds of general formula I I
  • Lg leaving group m 0 or 1 , where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 1 1 position, and the remaining variables R 3 , n and Y have the meaning according to general formula I shown above and preferred embodiments thereof, which comprises reacting a compound of general formula I or preferred embodiments thereof as described above or reacting a compound prepared according to the aforementioned process or preferred embodiments of said process with a compound Cu(Lg)2 in the presence of a polar solvent under confined conditions and temperatures between 20°C and 140°C.
  • Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate, m 0 or 1 , where in the case of m equal 1 the one Lg is bound either to the 8 or 9
  • confined conditions refers to reaction conditions in which the reactants during the reaction are placed in a tightly sealed reaction vessel, ampoule or the like.
  • Polar solvent typically refers to a solvent which is readilly miscible with water.
  • polar solvent is meant to embrace mixtures of polar solvents as well. Suitable polar solvents are e.g. water, dimethyl formamide (DMF), tetrahydofuran (THF), 1 ,4-dioxan, short carbon chain alcohols like e.g. butanol, i-butanol, tert.-butanol, propanol, i-propanol, ethanol or methanol and mixtures thereof.
  • DMF dimethyl formamide
  • THF tetrahydofuran
  • 1 ,4-dioxan short carbon chain alcohols like e.g. butanol, i-butanol, tert.-butanol, propanol, i-propanol, ethanol or methanol and mixtures thereof.
  • the leaving group Lg can be any group known to a person skilled in the art as being prone to easily leave the molecule.
  • Lg consists of or comprises strongly electron- withdrawing atoms or moieties and, thus, is normally split off as anionic species.
  • Preferred groups Lg are chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate and triflate which, in view of the aforesaid, leave the molecule as chloride, bromide, iodide, brosylate, nosylate, tosylate, mesylate ("mes" - H3C-SO3 " ) or triflate ("tri” - F3C-SO3 " ) anion.
  • brosylate brosylate
  • nosylate nosylate
  • tosylate tosylate
  • preferred reagents Cu(Lg)2 are CuC , CuBr2, Cub, Cu(bros)2, Cu(nos)2, Cu(tos)2,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
  • R12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein is -COOM, -SOsM or -P0 3 M,
  • M hydrogen, alkali metal cation or [NR ' ] 4+ , hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate, m 0 or 1 , where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 1 1 position,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, alkoxy, aryloxy,
  • R 12 alkyl, or a moiety of formula -Z-A, wherein
  • A is -COOM
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene.
  • a further objective of the instant invention is a process for the preparation of compounds of general formula III
  • R 1 , R 2 independently of each other a moiety of formula Ilia
  • R 5 independently of each other aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 2 is bound either to the 8 or 9 position of the perylene skeleton, and the remaining variables R 3 , n and Y have the aforementioned meaning according to general formula II and its preferred embodiment comprising reacting a compound of general formula II or its preferred embodiment with a compound or a mixture of compounds of general formula Ilia *
  • R 4 , R 5 independently of each other moieties of formulae lb or lc
  • R 6 hydrogen, alkyl, aryl, alkoxy, alkylthio or -NR 7 R 8 , where in case of two or more
  • R 7 to R 11 hydrogen, alkyl, cycloalkyl, aryl or hetaryl, and the remaining variables R 3 , n and Y have the aforementioned meaning according to general formula II and its preferred embodiment.
  • the Buchwald-Hartwig amination reaction is a well established synthetic route and the reaction conditions can easily be determined by a person skilled in the art. Conversion of aryl bromides to arylamines is specifically addressed in the publication by Guram, A.S.; Rennels, R.A.;
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy,
  • R12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SOsM or -P0 3 M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • R 4 , R 5 independently of each other aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 the respective R 2 is bound either to the 8 or 9 position of the perylene skeleton,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, alkoxy, aryloxy,
  • R 2 alkyl, or a moiety of formula -Z-A, wherein
  • A is -COOM
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene.
  • R 4 m 0 or 1 , where in the case of m equal 1 R 2 is bound either to the 8 or 9 position of the perylene skeleton,
  • R 4 , R 5 independently of each other moieties of formulae lb or lc
  • R 6 hydrogen, alkyl, aryl, alkoxy, alkylthio or -NR 7 R 8 , where in case of two or more substituents (p equal or greater than 2) these may be identical or different,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy,
  • R 12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl, or a moiety of formula -Z-A, wherein is -COOM, -SOsM or -P0 3 M,
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • R 6 hydrogen, alkyl, aryl, alkoxy, alkylthio or -N R 7 R 8 , where in case of two or more substituents (p equal or greater than 2) these may be identical or different, p 0, 1 , 2, 3, 4 or 5,
  • R 7 to R 1 1 hydrogen, alkyl, cycloalkyi, aryl or hetaryl,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, alkoxy, aryloxy, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4
  • R 12 alkyl, or a moiety of formula -Z-A, wherein A is -COOM,
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene.
  • a further objective of the instant invention is a process for the preparation of compounds of general formula IV (R 3 In
  • R 13 , R 14 independently of each other aryl or hetaryl, leaving group, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton, and the remaining variables R 3 , n and Y have the meaning according to general formula I and its preferred embodiments, which comprises reacting a compound of general formula I or preferred embodiments of such compounds with compounds of general formula Lg-R 13 and Lg-R 14 in the presence of a palladium containing catalyst under the conditions of the Suzuki coupling reaction.
  • R 13 , R 14 independently of each other moieties of formulae IVa or IVb
  • R15 hydrogen, alkyl, aryl, alkoxy, alkylthio or -NR 16 R 17 , where in case of two or more substituents (q equal or greater than 2) these may be identical or different, q 0, 1 , 2, 3, 4 or 5,
  • R 20 hydrogen, alkyl, aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton, and the remaining variables R 3 , n and Y have the meaning according to general formula I and the preferred embodiments thereof.
  • a further objective of the instant invention are compounds of general formula IV
  • R 13 , R 14 independently of each other aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R 13 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4
  • Y oxygen or NR 12 and R 12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SO3M or -PO3M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • a further objective of the instant invention are compounds of general formula IV
  • R 13 , R 14 independently of each other aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R 13 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4
  • R 12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SO3M or -PO3M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • R 13 , R 14 independently of each other aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R 13 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, alkoxy, aryloxy, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4 Y oxygen or N R 12 , and
  • R 12 alkyl, or a moiety of formula -Z-A, wherein is -COOM,
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different,
  • Ci-C6-alkylene or 1 ,4-phenylene isoethylene
  • R 13 R 14 independently of each other moieties of formulae IVa or IVb
  • R 15 hydrogen, alkyl, aryl, alkoxy, alkylthio or -NR 16 R 17 , where in case of two or more substituents (q equal or greater than 2) these may be identical or different, q 0, 1 , 2, 3, 4 or 5, X C(R 18 R 19 ) 2 , N R 20 , oxygen or sulfur,
  • R 16 to R 20 hydrogen, alkyl, aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R 13 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino, n 0, 1 , 2, 3 or 4
  • R 12 hydrogen, alkyl, cycloalkyi, aryl or hetaryl, or a moiety of formula -Z-A, wherein
  • A is -COOM, -SOsM or -P0 3 M
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different, and
  • Ci-C6-alkylene or 1 ,4-phenylene where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
  • R 15 hydrogen, alkyl, aryl, alkoxy, alkylthio or -NR 16 R 17 , where in case of two or more substituents (q equal or greater than 2) these may be identical or different,
  • R 16 to R 20 hydrogen, alkyl, aryl or hetaryl, m 0 or 1 , where in the case of m equal 1 R 14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R 13 ,
  • R 3 identical or different radicals hydrogen, alkyl, cycloalkyi, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
  • R12 alkyl or a moiety of formula -Z-A, wherein
  • A is -COOM
  • R ' hydrogen or alkyl, where the radicals R ' may be identical or different,
  • Ci-C6-alkylene or 1 ,4-phenylene.
  • a further objective or the instant invention is the use of compounds of general formula I I prepared according to abovementioned process and its preferred embodiments, of compounds of general formula II I prepared according to the abovementioned process and its preferred embodiments, of compounds of general formula IV prepared according to the abovementioned process and its preferred embodiments, of compounds of general formula I I and their preferred abovementioned embodiments, of compounds of claim 12 and their preferred abovementioned embodiments and of compounds of general formula IV and their preferred abovementioned embodiments for the preparation of dye-sensitized solar cells.
  • a further objective or the instant invention is a dye-sensitized solar cell comprising compounds of general formula II I prepared according to the abovementioned process and its preferred embodiments, compounds of general formula IV prepared according to the abovementioned process and its preferred embodiments, compounds of general formula II and their preferred abovementioned embodiments, compounds of claim 12 and their preferred abovementioned embodiments or compounds of general formula IV and their preferred abovementioned embodiments.
  • alkyl, aryl or heteroaryl represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl.
  • Alkyl comprises straight-chain or branched alkyl.
  • Alkyl is preferably Ci-C3o-alkyl, especially Ci- C2o-alkyl and most preferably Ci-Ci2-alkyl.
  • alkyl groups are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n- octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • branched alkyl groups can be represented by the following formula
  • R a is selected from Ci- to C28-alkyl, where the sum of the carbon atoms of the Rs
  • radicals is an integer from 2 to 29.
  • R a radicals are preferably selected from Ci- to Ci2-alkyl, especially Ci- to Cs-alkyl.
  • Preferred branched alkyl radicals of the above formula are, for example:
  • 1-pentadecyloctacosanyl 1-tetradecyloctacosanyl, 1-tridecyloctacosanyl, 1-dodecyloctacosanyl, 1-undecyloctacosanyl, 1-decyloctacosanyl, 1-nonyloctacosanyl, 1-octyloctacosanyl, 1- heptyloctacosanyl, 1-hexyloctacosanyl, 1-pentyloctacosanyl, 1-butyloctacosanyl, 1- propyloctacosanyl, 1-ethyloctacosanyl, 1-methyloctacosanyl.
  • AlkyI also comprises alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, -CO-, -NR b -, -SO- and/or -SO2- where R b is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below.
  • Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1,2,3,4,5 or more than 5) substituents. These are preferably each independently selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
  • Aryl-substituted alkyl radicals have at least one unsubstituted or substituted aryl group, as defined below.
  • the alkyl group of the aralkyi radical may bear at least one further substituent and/or be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, -CO-, - NR b -, -SO- and/or -SO2- where R b is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, more preferably phenyl-Ci-C4-alkyl, for example benzyl, 1 -phenethyl, 2-phenethyl, 1 -phenprop-1-yl, 2-phenprop-1 -yl, 3-phenprop-1 -yl, 1 -phenbut-1 -yl, 2- phenbut-1 -yl, 3-phenbut-1 -yl, 4-phenbut-1 -yl, 1 -phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl,
  • Halogen-substituted alkyi groups comprise a straight-chain or branched alkyi group in which at least one hydrogen atom or all hydrogen atoms are replaced by halogen.
  • the halogen atoms are preferably selected from fluorine, chlorine and bromine, especially fluorine and chlorine.
  • haloalkyi groups are especially chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl,
  • unsubstituted and substituted alkyi radicals which may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, -NR b -, -CO-, -SO- and/or -
  • dicyclopentylamino dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino; formylamino, acetylamino, propionylamino and benzoylamino; carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butyl- aminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl,
  • octylaminocarbonyl nonylaminocarbonyl, decylaminocarbonyl and phenylamino-carbonyl; aminosulfonyl, n-dodecylaminosulfonyl, ⁇ , ⁇ -diphenylaminosulfonyl, and
  • N,N-bis(4-chlorophenyl)aminosulfonyl methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy)carbonyl and
  • dodecyloxysulfonyl and octadecyloxysulfonyl dodecyloxysulfonyl and octadecyloxysulfonyl.
  • cycloalkyi denotes a cycloaliphatic radical having preferably 3 to 10, more preferably 5 to 8, carbon atoms.
  • Examples of cycloalkyi groups are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Substituted cycloalkyi groups may, depending on the ring size, have one or more (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyi, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. In the case of substitution, the cycloalkyi groups preferably bear one or more, for example one, two, three, four or five, Ci-C6-alkyl groups.
  • substituted cycloalkyi groups are especially 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec.
  • substituted and unsubstituted cycloalkyi groups are cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclo-pentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and 4- isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert- butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methyl-cycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-iso-propylcycloheptyl, 3- and 4-butylcycloheptyl,
  • aryl comprises mono- or polycyclic aromatic hydrocarbon radicals and monocyclic aromatic hydrocarbon radicals which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings.
  • Aryl has preferably 6 to 14, more preferably 6 to 10, carbon atoms. Examples of aryl are especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl and pyrenyl, especially phenyl, naphthyl and fluorenyl.
  • Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyi, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
  • the alkyi, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents on the aryl may in turn be unsubstituted or substituted.
  • the substituents on the aryl are preferably selected from alkyi, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro.
  • Substituted aryl is more preferably substituted phenyl which generally bears 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, substituents.
  • Substituted aryl is preferably aryl substituted by at least one alkyi group ("alkaryl").
  • Alkaryl groups may, depending on the size of the aromatic ring system, have one or more (e.g. 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyi substituents.
  • the alkyi substituents may be unsubstituted or substituted. In this regard, reference is made to the above statements regarding unsubstituted and substituted alkyi.
  • the alkaryl groups have exclusively unsubstituted alkyi substituents.
  • Alkaryl is preferably phenyl which bears 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, alkyi substituents.
  • Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6- diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6- dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and
  • hetaryl comprises heteroaromatic, mono- or polycyclic groups and monocyclic groups which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings.
  • ring carbon atoms these have 1 , 2, 3, 4 or more than 4 of the ring heteroatoms.
  • the heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur.
  • the hetaryl groups have preferably 5 to 18, e.g. 5, 6, 8, 9, 10, 1 1 , 12, 13 or 14, ring atoms.
  • Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), selenophen-2- yl, selenophen-3-yl, 1 H-pyrrol-2-yl, 1 H-pyrrol-3-yl, pyrrol-1 -yl, imidazol-2-yl, imidazol-1 -yl, imidazol-4-yl, pyrazol-1 -yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5- isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazoly
  • Polycyclic hetaryl has 2, 3, 4 or more than 4 fused rings.
  • the fused-on rings may be aromatic, saturated or partly unsaturated.
  • Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxadiazolyl; benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl,
  • thienothiophenyl thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophenyl, naphtho[2,3-b]thiophenyl, naphtha[2,3-b]furyl, dihydroindolyl,
  • dihydroindolizinyl dihydroisoindolyl, dihydroquinolinyl, dihydroisoquinolinyl.
  • Substituted heteroaryls may, depending on the number and size of their ring systems, have one or more (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • the substituents are preferably selected from Ci-C6-alkyl, Ci-C6-alkoxy, hydroxyl, carboxyl, halogen and cyano.
  • Halogen represents fluorine, chlorine, bromine or iodine, preferably chlorine and bromine.
  • Alkali cation represents sodium, potassium, rubidium and cesium, preferably sodium and potassium.
  • R ' in the tetraalkyl ammonium cation [NR ' ] 4+ typically refers to methyl or tert.-butyl.
  • DSCs generally comprise the following elements: an electrically conductive layer (being part of or forming the working electrode or anode), a photosensitive layer generally comprising a semi- conductive metal oxide and a photosensitive dye, a charge transfer layer and another electrically conductive layer (being part of or forming the counter electrode or cathode).
  • N-(1 -ethylpropyl)-2,5-bis[3,3-dimethylbutyl]perylene-3,4-dicarboxylic acid monoimide (0.100 g, 0.179 mmol), bis(pinacolato)diboron (0.100 g, 0.393 mmol), [lr(OMe)cod] 2 (bis(1 ,5- cyclooctadiene)dimethoxydiiridium; 5.9 mg, 8.9 ⁇ ) and dtbpy (4,4'-di-tert-butyl-2,2'-bipyridyl; 4.8 mg, 17.9 ⁇ ) were mixed in an oven dried flask under argon atmosphere.
  • UV-vis(in toluene) A max (e [M- crrv 1 ]): 481 nm (2.98 x 10 4 M- crrv 1 ), 509 nm (2.83 x 10 4 M- crrv 1 ).
  • the monoborylated compound also according to general formula I of the present invention
  • N-(1 -ethylpropyl)-8,1 1 -bis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial . Copper(ll) bromide (2.08 g, 9.33 mmol) was added, the vessel sealed and heated up to 120°C for 12 hours. The reaction mixture was poured into 200 mL of 1 .0 M hydrochloric acid and filtered to obtain a red solid.
  • UV-vis(in toluene) A ma x (e [M- 1 crrv 1 ]): 495 nm (3.21 x 10 4 M- 1 crrv 1 ), 466 nm (2.45 x 10 4 M- 1 crrv 1 ).
  • the monobrominated compound (also according to general formula II of the present invention)
  • N-(1 -heptyloctyl)-8,1 1 -bis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (1 .00 g, 1 .28 mmol) was suspended in a mixture of THF (90 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial . Copper(ll) bromide (2.85 g, 12.8 mmol) was added, the vessel sealed and heated up to 120°C for 12 hours. The reaction mixture was poured into 200 mL of 1 .0 M hydrochloric acid and filtered to obtain a red solid.
  • N-(1 -ethylpropyl)-8,1 1 -bis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial . Copper(ll) chloride (1 .254 g, 9.33 mmol) was added, the vessel sealed and heated up to 120°C for 12 hours. The reaction mixture was poured into 200 mL of 1 .0 M hydrochloric acid and filtered to obtain a red solid.
  • UV-vis(in toluene) A max (e [M- crrr 1 ]): 494 nm (2.61 x 10 4 M- crrv 1 ), 465 nm (2.00 x 10 4 M- crrr 1 ).
  • the monochlorinated compound (also according to general formula II of the present invention)
  • IR spectrum (ATR) Amax [cm- 1 ] 3034, 2953, 2874, 2691 , 1652, 1593, 1566, 1500, 1457, 1349, 1268, 1246, 1 197, 1085, 808, 751 .
  • IR spectrum (ATR) Amax [cm- 1 ] 2954, 2873, 1692, 1654, 1593, 1564, 1507, 1461 , 1351 , 1254, 1085, 1015, 805, 752.
  • IR spectrum (ATR) Amax [cm- 1 ] 2951 , 2901 , 2871 , 1697, 1662, 1593, 1561 , 1506, 1365, 1250, 1 172, 1 132, 1013, 821 , 755.
  • reaction mixture was purifed via gel permeation chromatography to separate mono- and difunctionalised product with chloroform and via column chromatography with dichloromethane. Yield: 50 mg brown solid (4 %) of compound C10.
  • IR spectrum (ATR) Amax [cm- 1 ] 3630, 3499, 3058, 2957, 2923, 2860, 1750, 1691 , 1651 , 1591 , 1570, 1448, 1407, 1370, 1292, 1247, 1 172, 1073, 1020, 970, 853, 799, 755, 736.
  • ⁇ ⁇ 2 blocking layer was prepared on a fluorine-doped tin oxide (FTO)-covered glass substrate using spray pyrolysis (cf. B. Peng, G. Jungmann, C. Jager, D. Haarer, H. W. Schmidt, M. Thelakkat, Coord. Chem. Rev. 2004, 248, 1479).
  • a ⁇ 2 paste (Dyesol), diluted with terpineol, was applied by screen printing, resulting in a film thickness of 1.7 ⁇ .
  • Fabrication of the device was completed by evaporation of 200 nm of silver as the counter electrode.
  • the active area of the sDSC was defined by the size of these contacts (0.13 cm 2 ), and the cells were masked by an aperture of the same area for measurements.
  • the current-voltage characteristics for all cells were measured with a Keithley 2400 under 1000 W/m 2 , AM 1 .5G conditions (LOT ORIEL 450 W).
  • the incident photon to current conversion efficiency's (IPCE) were obtained with an Acton Research Monochromator using additional white background light illumination.
  • the samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp.
  • the power of the incident light beam was (2-5)-10 -8 W.
  • the negative voltage of -300 V was supplied to the sample substrate.
  • the counter-electrode with the 4.5x15 mm 2 slit for illumination was placed at 8 mm distance from the sample surface.
  • the counter-electrode was connected to the input of the BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement.
  • the 10 "15 - 10 "12 A strong photocurrent was flowing in the circuit under illumination.
  • the photocurrent J is strongly dependent on the incident light photon energy hv.

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EP13828249.6A 2012-08-06 2013-07-24 Borhaltige perylenmonoimide, verfahren zu deren herstellung, deren verwendung als bausteine zur herstellung von perylenmonoimidderivaten, monoimidderivate und deren verwendung bei farbstoffsensibilisierten solarzellen Withdrawn EP2880018A4 (de)

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