WO2012107488A2 - Photosensibilisateurs exempts de métal - Google Patents

Photosensibilisateurs exempts de métal Download PDF

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WO2012107488A2
WO2012107488A2 PCT/EP2012/052127 EP2012052127W WO2012107488A2 WO 2012107488 A2 WO2012107488 A2 WO 2012107488A2 EP 2012052127 W EP2012052127 W EP 2012052127W WO 2012107488 A2 WO2012107488 A2 WO 2012107488A2
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group
mmol
electron
solution
compound
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WO2012107488A3 (fr
Inventor
Stefano Maiorana
Emanuela LICANDRO
Elena LONGHI
Silvia Cauteruccio
Alessandro Abbotto
Clara Baldoli
Filippo De Angelis
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Consiglio Nazionale delle Richerche CNR
Universita degli Studi di Milano
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Consiglio Nazionale delle Richerche CNR
Universita degli Studi di Milano
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    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/008—Triarylamine dyes containing no other chromophores
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention describes photosensitizers free from metal ions, which are used for manufacturing photovoltaic cells.
  • a solar cell as shown in Figure 1, comprises a light- absorbing component (photosensitizer) (a) , a semiconductor material (b) , typically titanium dioxide, on which the light- absorbing compound is adsorbed, a charge carrier component (electrolyte) (c) , a working electrode (d) , and a typically opaque counter electrode (e) .
  • a light- absorbing component photosensitizer
  • a semiconductor material typically titanium dioxide, on which the light- absorbing compound is adsorbed
  • a charge carrier component electroactive metal
  • electrostatic electrode electrolyte
  • working electrode a typically opaque counter electrode
  • e typically opaque counter electrode
  • the present invention describes metal-free photosensitizers of the push-pull type.
  • Figure 1 represents a simplified draft of a photoelectrochemical solar cell
  • Figures 2A and 2B show the synthesis reaction of intermediates according to the present invention
  • Figures 3 and 4 show the synthesis of compounds according to the present invention
  • Figure 5 shows the JV curve related to cell Bl
  • Figures 6 and 7 illustrate the JV curves of the measurements carried out 4 days after the cell sealing.
  • the present invention describes organic photosensitizing/light- absorbing compounds free of metal ions.
  • A is an electron-withdrawing group
  • L is a spacer
  • GD is an electron-donating group
  • R 3 and R 4 are selected from among the group comprising hydrogen, -R 5 or -OR 5 , where R 5 is a Ci-Cio linear or branched alkyl chain.
  • the GD group is a group of formula
  • R and R 1 are selected from among the group comprising
  • R 3 and R 4 may be H, -R 5 or -OR 5 , where R 5 is a Ci-Cio linear or branched alkyl chain; and comprising wherein R 6 is H or a -R 5 or -OR 5 group, wherein R 5 is a Ci-Cio linear or branched alkyl chain.
  • the compounds of the invention have the following formulas:
  • the compound preparation comprises the steps of:
  • GD-X' (II) group where GD is the above-described electron-donating group carrying a reactive group X' able to condense or to couple with a X-L-Y (III) group, precursor of a dibenzothiophene spacer group L carrying a reactive group X able to condense or to couple with a molecule (II), precursor of GD, generating R2, and Y is a reactive group precursor of an electron-withdrawing substrate- linking group, as reported in the following reaction:
  • reactive groups X able to condense or couple with a GD precursor molecule are represented by a -C ⁇ CH triple bond or by a -CHO aldehyde residue.
  • X' groups these are preferably represented by a halogen group, selected from among chlorine, fluorine, bromine and iodine, where iodine is the preferred halogen group, or by other suitable condensing groups.
  • a halogen group selected from among chlorine, fluorine, bromine and iodine, where iodine is the preferred halogen group, or by other suitable condensing groups.
  • a preferred example of condensing group is represented by triphenylphosphonium.
  • a GD-X' group where X' is a halogen, shall react with a X-L-Y group where X is a triple bond.
  • a GD-X' group where X' is triphenylphosphonium shall react with a X-L-Y group where X is an aldehyde group.
  • the conversion may occur (i) by oxidizing group Y to A, or (ii) by condensing group Y with a molecule A-Y' comprising acid hydrogen atoms such as, for example, cyanoacetic acid, or iii) by coupling GD-R.2-L-Y with groups
  • Y is an aldehyde group
  • the corresponding carboxylic derivative will be obtained.
  • this generally comprises the step of c) reacting the precursor L-3 ⁇ 4 of the spacer group with a precursor Y' ' ' of a reactive group Y according to the following reaction H-L-H (V)+ Y''' (VI) - H-L-Y (VII) d) reacting the intermediate H-L-Y (VII) with a precursor X-X' ' of the reactive group able to condense or to couple with a molecule precursor of GD, according to the following reaction:
  • the reactive group Y in the intermediate (VII) of step c) is an aldehyde group and a suitable precursor thereof ⁇ ' ' ' is represented by N-formylpiperidine or dimethylformamide (DMF) .
  • a suitable reactant X-X' ' is represented, for example, by trimethylsilylacetylene or N- formylpiperidine or DMF and, therefore, X will be a -C ⁇ CH triple bond or a -CHO aldehyde residue, as described above.
  • the reactive group Y and the reactive group X are equal to each other.
  • the preparation of the OHC-L-CHO (IX) group will comprise a single step c' ) of reacting H-L-H with a molecule precursor of the aldehyde group in suitable reaction conditions according to the following reaction : c' ) H-L-H + Y" ' - OHC-L-CHO (IX)
  • Y' ' ' is represented, for example, by N- formylpiperidine or DMF.
  • compound 74e can also be obtained by performing a McMurry coupling as illustrated in Figure 2B.
  • said process comprises the steps of:
  • a suitable starting 1- ( thiophen-2-yl ) alkyl-l-one is 1- ( thiophen-2-yl ) butan-l-one as disclosed in the following Example 13.
  • the photosensitizing/light-absorbing compounds of the invention may be used for manufacturing reference photoelectrochemical devices (described, for example, by Graetzel, M. Nature 2001, 414,338), photoelectric conversion devices, photovoltaic devices and/or solar cells .
  • Preparing photoelectrochemical solar cells will comprise the step of making a semiconductor material, typically represented by monolayer or multilayer titanium dioxide, adsorb a solution comprising one or more compounds of the present invention.
  • a semiconductor material typically represented by monolayer or multilayer titanium dioxide
  • said solution has a concentration ranging from about 1CT 4 to about 1CT 3 M.
  • a solution of chenodeoxycholic acid in a concentration ranging from about lCT 4 to about 1CT 3 M is added to the solution of one or more light-absorbing compounds.
  • Photoelectrochemical solar cells thus obtained revealed the properties of the above- described compounds to convert solar energy into electric energy, with significant performances at this step of technological development.
  • UV-vis (10 ⁇ 5 in CH 2 C1 2 ): A max 240; 277; 330; 387 2 ) 6-Bromobenzo [ 1 , 2-b : 4 , 5-b' ] dithiophene-2- carboxaldehyde (6)
  • N-iodosuccinimmide (1.44 mmol) are added to a solution of bis ( 4-metoxyphenyl ) amine
  • the product 8 is obtained as 500 mg (90% yield) of a transparent rose-colored oil.
  • UV-vis (10 ⁇ 5 in CH 2 C1 2 ): A max ( ⁇ , NT 1 cm -1 ) 288 (9722), 330 (12278), 332 (12222). 2 ) 2-cyano-3- ⁇ 6- [ 4- (bis ( 4-metoxyphenylamino ) phenylethynyl ] benzo [ 1 , 2-b : 4 , 5-b' ] dithiophene-2-yl ⁇ acrylic acid (1)
  • UV-vis (10 ⁇ 4 in CH 2 C1 2 ): A max ( ⁇ , M ⁇ cnf 1 ) 299 (6076) , 368 (9495) .
  • 6-ethynylbenzo [ 1 , 2-b : 4 , 3-b' ] dithiophene-2- carboxyaldehyde 10 is synthesized from benzo[l,2- b : 4 , 3-b' ] dithiophene-2-carboxyaldehyde following the same procedures as indicated for the synthesis of compound 3.
  • the electron-donating intermediate (11) may be prepared according to what has been described by Haining, T et al (Haining, T . ; Xichuan, Y.; Ruikui, C; Rong, Z . ; Anders, H. ; Licheng, S.; J. Phys. Chem. , 2008, 11023) according to the reaction scheme below.
  • the intermediate of formula (14) may be prepared according to what has been described by Makromolek . Chem. 1983, 184, 627-650 or as reported in the following reaction scheme.
  • the combined organic phases are dried on Na 2 SC> , filtered and the solvent is evaporated at reduced pressure.
  • the crude reaction product is purified by silica gel column chromatography (CH 2 Cl 2 /hexane, 9:1).
  • the desired product 15 is obtained as 50.2 mg (63%) of a red solid.
  • Compound 52 was synthesized following the same procedure of 2, starting from 70 mg (0.13 mmol) of 26 to give 46 mg (55%) of 52 as a red solid.
  • Compound 44 was synthesized following the same procedure of 11, starting from 115 mg (0.23 mmol) of 49 (as described in Kim, Chulwoo; Choi, Hyunbong; Kim, Sanghoon; Baik, Chul; Sang, Ook Kang; Ko, Jaejung; Song, Kihyung; Kang, Moon-Sung J. Org. Chem., 2008, 73 (18) 7072 - 7079) to give 190 mg of 44, which was used, without further purification, for the subsequent step.
  • Compound 43 was synthesized following the same procedure of 15, starting from 64 mg (0.26 mmol) of 14 and 180 mg of 44 to give 82.4 mg (53%) of 43 as an orange solid, after purification over column chromatography (CH 2 Cl 2 /hexane, 4:6).
  • Compound 28 was synthesized following the same procedure of 11, starting from 270 mg (0.80 mmol) of 34 (as described in Davies, Joshua A.; Elangovan, Arumugasamy; Sullivan, Philip A.; Olbricht, Benjamin C; Bale, Denise H. ; Ewy, Todd R. ; Isborn, Christine M.; Eichinger, Bruce E . ; Robinson, Bruce H. ; Reid, Philip J.; Li, Xiaosong; Dalton, Larry R. J. Am. Chem. Soc. 2008, vol. 130(32), 10565 - 10575) to give in 400 mg of 28 as a green solid (97% yield) . P. f . : 78-83 °C.
  • UV-vis CH2CI2 (1.08-10 321 nm (1.84 -10 4 M ⁇ 1 cm 1 ) , 345 nm 1.78 -10 M cm 477 nm (3.92 -10 " cm
  • Chenodeoxycholic acid was added to both solutions as disaggregating at a concentration of 4-1CT 3 M.
  • the four photoanodes (0.20 cm 2 , a single coat of Dyesol 18NR-A0 treated with TiCl 4 0.04 M) were immersed for a time period of 18 hours in the above- mentioned solutions (two anodes for solution) .
  • the IV curves reporting the conversion data were recorded at an incident radiation power of 0.94 sun (94 mW/cm 2 ) .
  • J sc maximum density of obtainable photocurrent, measured under short circuit (mA/cm 2 ) conditions
  • VQ C maximum obtainable potential, measured under open circuit ( V ) conditions ;
  • FF fill factor, which is obtained from the ratio between Jm P xV mp and J sc xV 0 c, where J mp is the photocurrent density at the maximum power value and V mp is the cell potential at the maximum power value;
  • ⁇ light energy conversion efficiency - electric energy (%), measured under standard lighting conditions PM 1.5 corresponding to 100 mW/cm 2 or 1000 W/m 2 , obtained applying the following relation:
  • Figure 5 shows the JV curve obtained for cell Bl, exhibiting the best efficiency for compound 1.
  • Two cells (A and B) were made using the following procedure .
  • a solution 2-1CT 4 M of photosensibilizer 2 in CH 3 CN was prepared with the addition of chenodeoxycholic acid at a concentration of 3-1CT 3 M.
  • the photoanode (0.20 cm 2 , a single coat of Dyesol 18NR-A0 treated with TiCl 4 0.04 M) was immersed in the photosensibilizer solution for 6 hours.
  • the commercial electrolyte Iolitech ES-0004-HP was used with the addition of Lil at a 0, 06 M concentration.
  • an Ag conductive alloy was laid on the electrodes.
  • Reported parameters are those which were measured immediately after sealing (0 days) and 3 and 4 days after assembling regarding two cells (A, B) made under the same conditions.
  • Data measured after three days also comprise Ag contacts .
  • Figures 5 and 6 show JV curves, respectively obtained for cells A and B, measured 4 days after sealing.
  • the compounds of the invention are particularly advantageous from an economical point of view, since they can be prepared at a lower cost. In addition, their disposal is simpler, cheaper and less harmful for the environment . Furthermore, since they are chemically stable over time, the compounds of the invention are particularly useful and advantageous.
  • Electrolyte 1.0 M dimethyl imidazolium iodide, 0.03 M 12, 0.05 M Lil, 0.1 M guanidinium thiocyanate, 0.5 M 4- t-butylpyridine in acetonitrile/valeronitrile 85: 15.
  • CONDITIONS B Double layer of transparent 20 nm nanoparticles T1O 2 with a scattering layer of 150-250 nm nanoparticles T1O 2 (total thickness 15 ⁇ ) .
  • the starting compound 1- ( thiophen-2-yl ) butan-l-one ( 71 ) was prepared according to the literature (Sundby, E . ; Andersen, M. M.; Hoff, B. H. ; Anthonsen,
  • T1CI 4 (3.0 mL, 27.2 mmol, 1.2 equiv) was added dropwise to a solution of ketone 71 (3.5 g, 22.6 mmol) in dry THF (55 mL) at -20°C. After 30 min at -20°C, Zn powder (3.7 g, 56.6 mmol, 2.5 equiv) was added in 6 portions in 10 min, and then the mixture was refluxed for 3.5 h. Ice- water (40 mL) and an aqueous solution of HC1 (IN, 40 mL) were added at room temperature.
  • N-bromosuccinimide (0.270 g, 1.52 mmol, 2.1 equiv) was added to a solution of 72 (0.200 g, 0.723 mmol) in dry DMF (2 mL) under ice-water bath. The mixture was stirred in the dark at room temperature and the progress of the reaction was monitored by TLC (hexane) . After 3 h, the mixture was quenched with water (10 mL) and the aqueous phase was extracted into CH2CI2 (3 x 10 mL) . The organic phase was washed with water and dried with Na2SC> .
  • the alkene 73a (0.185 g, 0.427 mmol) was dissolved in dry CH 2 CI 2 (60 mL) , and the solution was constantly sparged with nitrogen. After 10 min, FeCl 3 (0.277 g, 1.70 mmol, 4 equiv) was added to the solution at room temperature, and the resulting mixture was stirred under a nitrogen purge. The progress of the reaction was monitored by HPLC (MeCN/H 2 0, 9:1) . After 2 h, methanol (approx. 50 mL) was added and the reaction mixture was stirred for 30 min. The mixture was concentrated under reduce pressure, and the crude product was purified by chromatography on silica gel (hexane) to give 74a as a white solid (0.139 g; 76 %) .
  • the alkene 73b (0.141 g, 0.267 mmol) was dissolved in dry CH 2 CI 2 (50 mL) , and the solution was constantly sparged with nitrogen. After 10 min, FeCl 3 (0.173 g, 1.07 mmol, 4 equiv) was added to the solution at room temperature, and the resulting mixture was stirred under a nitrogen purge. The progress of the reaction was monitored by HPLC (MeCN/H 2 0, 9:1) . After 1.5 h, methanol (approx. 50 mL) was added and the reaction mixture was stirred for 30 min.
  • the alkene 73d (0.050 g, 0.150 mmol) was dissolved in anhydrous dichloroethane (30 mL) , and the resulting solution was heated to 80 °C. After 10 min, FeCl 3 (0.100 g, 0.601 mmol, 4 equiv) was added to the solution at 80° C, and the resulting mixture was stirred under a nitrogen purge. The progress of the reaction was monitored by HPLC (MeCN/H 2 0, 9:1) . After 5 h, the mixture was cooled to room temperature and quenched with methanol (approx. 30 mL) .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
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Abstract

La présente invention porte sur des photosensibilisateurs organiques exempts de métal et sur leur procédé de préparation. La présente invention porte également sur l'utilisation de tels composés pour la fabrication de photopiles.
PCT/EP2012/052127 2011-02-08 2012-02-08 Photosensibilisateurs exempts de métal Ceased WO2012107488A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2011A000184A IT1403920B1 (it) 2011-02-08 2011-02-08 Composti fotosensibilizzanti "metal free".
ITMI2011A000184 2011-02-08

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WO2012107488A2 true WO2012107488A2 (fr) 2012-08-16
WO2012107488A3 WO2012107488A3 (fr) 2013-01-10

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KR101465454B1 (ko) * 2012-11-13 2014-12-02 재단법인대구경북과학기술원 염료감응 태양전지용 유기염료 및 이를 포함하는 염료감응 태양전지
CN107033058A (zh) * 2017-05-17 2017-08-11 江苏斯威森生物医药工程研究中心有限公司 氮杂环高选择性醛的合成工艺
WO2017159657A1 (fr) * 2016-03-18 2017-09-21 Dic株式会社 Nouveau composé et matériau semi-conducteur organique le contenant
WO2024203704A1 (fr) * 2023-03-24 2024-10-03 富士フイルム株式会社 Élément de conversion photoélectrique, élément d'imagerie, capteur optique et composé
WO2024262437A1 (fr) * 2023-06-20 2024-12-26 富士フイルム株式会社 Élément de conversion photoélectrique, élément d'imagerie ainsi que procédé de fabrication de celui-ci, capteur optique, et composé

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JP3006329B2 (ja) * 1993-02-02 2000-02-07 富士電機株式会社 電子写真用感光体
JP2009059841A (ja) * 2007-08-31 2009-03-19 Mitsui Chemicals Inc 有機トランジスタ
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CN107033058A (zh) * 2017-05-17 2017-08-11 江苏斯威森生物医药工程研究中心有限公司 氮杂环高选择性醛的合成工艺
WO2024203704A1 (fr) * 2023-03-24 2024-10-03 富士フイルム株式会社 Élément de conversion photoélectrique, élément d'imagerie, capteur optique et composé
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