WO2016111636A1 - Dérivés de benzo[1,2-b:4,5-b]furane à titre de ligands de colorants au ruthénium et procédés pour les obtenir - Google Patents

Dérivés de benzo[1,2-b:4,5-b]furane à titre de ligands de colorants au ruthénium et procédés pour les obtenir Download PDF

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WO2016111636A1
WO2016111636A1 PCT/PL2015/000206 PL2015000206W WO2016111636A1 WO 2016111636 A1 WO2016111636 A1 WO 2016111636A1 PL 2015000206 W PL2015000206 W PL 2015000206W WO 2016111636 A1 WO2016111636 A1 WO 2016111636A1
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formula
ruthenium
ligand
complex
bis
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PCT/PL2015/000206
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Mariusz Jan BOSIAK
Marcin Michał PAKULSKI
Andrzej Jan WOLAN
Marcin RAKOWIECKI
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SYNTHEX TECHNOLOGIES Sp. z o.o.
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    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00

Definitions

  • the present invention relates to the Iigands comprising in their structure benzodifuran moiet and ruthenium complexes constructed on the basis on said Iigands and methods for their preparing, and use for DSSC thereof.
  • M. Gretzel and M.K. Nazeeruddin in US005463057A disclose a complex of two molecules of 2,2'-bipyridyl-4,4'-dicarboxylic acid (dcbpy) with ruthenium and isothiocyanate groups, having been converted into a tetrabutylammonium salt, for the purpose of improving the solubility in alcohols, water and the polar organic solvents, said complex is used as a photosensitizer of titanium oxide in the dye photovoltaic cells of DSSC type.
  • dcbpy 2,2'-bipyridyl-4,4'-dicarboxylic acid
  • ruthenium and isothiocyanate groups having been converted into a tetrabutylammonium salt
  • the mixed ruthenium complexes which comprise two different Iigands comp!exed to the ruthenium atom are also known.
  • IPCE incident photon-to-current conversion efficiency
  • incorporation of the thiophene system to the bipyridyl ligand may increase energy levels of metal center and LU O orbital of the ligand. Consequently, the absorption band derived from the passage of the "charge transfer" type from metal to ligand shifts toward longer wavelengths.
  • the subject of the present invention are novel ligands for the synthesis of the photosensitizing complexes of ruthenium for use in DSSC
  • Ri H, alkyl, alkene, aikyne, aromatic hydrocarbon, polyglycol, organic salt (e.g. tetrabutylammonium) and inorganic salt (e.g. sodium);
  • the subject of the invention are further new symmetric and asymmetric photosensitizing ruthenium complexes of the invention for use DSSC wherein
  • the subject of the invention is a method for the preparing a 6,6'-([2,2'- bipyridine]-4,4'-diyl)bis(2-methylbenzo[1 ,2-6:4, 5-6']difuran-3-carboxylic) acid ligand (1) of formula !
  • esters and salts thereof wherein said method comprises the steps of obtaining ligand 1 using the Sonogashira reaction of 4,4'-dihalo-2,2'-bipyridine with ethynyltrimethylsilane in a solvent, in the presence of a palladium catalyst, with or without addition of a phosphine, in the presence of copper halide and amine as a base; wherein removing the trimethylsilyl groups in the intermediate product is carried out without isolation thereof, with the use of fluoride or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, reacting resulted 4,4-diethynyl-2,2'-bipyridine without isolation thereof with an ester of 5- hydroxy-6-haIo-2-methyibenzofuran-3-carboxylic acid at room temperature or higher temperature to yield the Iigand of formula I, hydrolyzing thereof, if necessary, under basic or acid conditions and isolating using
  • Suitable solvents are aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrite, ether, alcohol, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents.
  • the solvent is selected from toluene, xylene, tetrahydrofuran, dimethyl sulfoxide, acetonitrile or 1 ,4-dioxane or mixture thereof.
  • the catalyst used according to the invention is a palladium compound selected from the group consisting of paliadium(!l) dihalides, palladium(ll) acetate, palladium(il) sulfate, bis(triphenylphosphine)paliadium(l[) dichloride, bis(tricyclopentyIphosphine)palladium(ll) dichloride, bis(tricyclohexylphosphine)- palladium(ll), bis(dibenzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), preferably [1 ,1'-bis (dipheny!phosphino) ferrocene]dichloropalladium(ll).
  • reaction is carried out with or without addition of aromatic or nonaromatic phosphine.
  • the reaction is carried out with the addition of a copper halide, preferably copper iodide.
  • the reaction is carried out in the presence of aliphatic, alicyclic, aromatic, heterocyclic amine, preferably diisopropylamine, at room temperature or higher temperature.
  • the method comprises the step of removing the trimethy!silyl groups from the intermediate without isolation thereof using organic or inorganic fluorides, or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, preferably tetrabutylammonium fluoride.
  • the method comprise step of reacting in the same flask resulting 4,4'-diethynyl-2,2'-bipyridine, without isolation thereof, with an ester of 5-hydroxy-6- halo-2-methyl-benzofuran-3-carboxylic acid. More preferably, reacting the resulting 4 J 4'-diethynyl-2,2'-bipyridine with 5- hydroxy-6-bromo-2-methyl-benzofuran-3-carboxylic acid ester or 5-hydroxy-6-iodo-2- methyi-benzofuran-3-carboxylic acid ester.
  • reaction of 4,4'-diethinylo-2,2 , -bipyridine with 5-hydroxy-6-iodo-2-methyl- benzofuran-3-carboxylic acid ester is carried out at room temperature or higher temperature, preferably at 80°C.
  • the subject of the invention is also a method for the preparing 6,6'-((1 ,1')- [3,3 , -bipyridine]-4,4'-diyibis(etheno-2,1-diyl))bis(2-methylobenzo[1 ,2-b:4,5- ⁇ ']-difuran- 3,7-dicarboxylic) acid ligand (2) of Formula II, according to the invention, and esters and salts thereof, wherein the method comprises the steps of obtaining the ligand 2 using the Wittig reaction of [2,2'-bipyridine]-4,4'-carbaldehyde with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-/):4,5-iti]difuran-2-yl)methyl)triphenyi- phosphonium halide in an organic solvent in the presence of a base, at room temperature or higher temperature, if necessary, hydrolyzing thereof under basic or acidic conditions and is
  • the suitable solvents are alcohol, hydrocarbon, aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
  • the sutiabte base are hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
  • the reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
  • the further subject of the invention is a method for the preparing 2-((5H- cyclopenta[1 ,2-0:5, 4-0']dipyridin-5-ylidene)methyl)-6-methylbenzo[1 ,2-jb:4,5-b']difuran- 3,7-dicarboxy!ic acid ligand (3) of the formula III according to the invention and esters and salts thereof, wherein the method comprises the steps for obtaining a ligand 3 using the Wittig reaction of 5H-cyclopenta[1 ,2-j :5,4-j ]dipyridin-5-one with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-0:4,5-/ ']difuran-2-yl)methyl)
  • tritriphenylphosphonium halide in a solvent, in the presence of a base, at room temperature or higher temperatureand which, if necessary, hydrolyzing thereof under basic or acidic conditions and isolating using a known method.
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
  • the suitable base is one of the hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
  • the reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
  • the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
  • the complex 4 is obtained in one process, without isolation of intermediates.
  • the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
  • the source of ruthenium is a dimer of dichloro(p-cymene) ruthenium(l!).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
  • the complex 5 is obtained in one process, without isolation of intermediates.
  • the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
  • the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
  • the complex 6 is obtained in one process, without isolation of intermediates.
  • the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
  • the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium (II).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably the suitable solvent is W,N-dimethylformamide.
  • the complex 7 is obtained in one process, without isolation of intermediates.
  • the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
  • the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably ⁇ , ⁇ -dimethylformamide.
  • the complex 8 can be obtained in one process, without isolation of
  • reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
  • the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
  • the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably A/,/V-dimethylformamide.
  • the complex 9 is obtained in one process, without isolation of intermediates.
  • the reaction is carried out at room or elevated temperature, preferably at a temperature of 140- 50°C.
  • Developed symmetric and asymmetric ruthenium complexes 3-9 show the absorption of visible light and UV with high molar extinction coefficients and can be used as dye for the production of DSSC (Dye-Sensitized Solar Cells). The products are stable in air and after exposure to sunlight.
  • the precursors for the synthesis of ligand 1 are the esters of 5-hydroxy-6- haio-2-methyl-benzofuran-3-carboxylic acid obtained in known bromination or iodination reactions of 5-hydroxy-2-methyl-benzofuran-3-carboxylic acid ester, wherein said ester can be obtained in known reaction of p-£>enzoquinone with ethyl acetoacetate in ethanol, treated by known transesterification reaction of an aliphatic, unsaturated, cyclic, aromatic alcohol, polyglycol, in acidic or alkaline conditions and separated by a known method, ethyny!trimethylsilane and 4,4'-dihalogeno-2,2'- bipyridine.
  • the precursors for the synthesis of !igand 2 are following: known 2,2'- bipyridine-4,4'-dikarboaldehyd and salts of ((3,7-bis(alkoxycarbonyl)-6-methylbenzo [1 , 2-0:4, 5-b]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters of 2-(halomethyl)-6-methylbenzo[1 ,2 ⁇ jb:4,5-0']difuran-3,7- dicarboxy!ic acid by reaction with triphenylphosphine in an organic solvent.
  • the precursors for the synthesis of ligand 3 are following: known 5H- cy openta-[1 ,2-6:5, 4-/b]dipyridin-5-one and salts of ((3,7 ⁇ bis(alkoxycarbonyl)-6- methyl[1 ,2b:4,5-jb]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters 2-(halomethyl)-6-methylbenzo[1 ,2-£>:4,5-J_>']difuran-3,7- dicarboxylic acid by reaction with triphenylphosphine in an organic solvent.
  • the precursors for the synthesis of complexes 4, 6, 8 are following: compounds 1-3, ruthenium(lil) chloride or a dimer of dichloro(p-cymene)ruthenium(!l), 2,2 , -bipyridine-4,4 , -dicarboxylic acid and inorganic thiocyanate.
  • the precursors for the synthesis of complexes 5, 7, 9 are following: the compounds 1-3, ruthenium(III) chloride or a dimer of dichloro(p-cymene)ruthenium(ll) and the inorganic thiocyanate.
  • a method for the preparing of 6,6 , -([2,2 , -bipyndine] ⁇ 4,4 , -diy])b!s (2- methylbenzo[1 , 2-0:4, 5-i>']difuran-3-carboxylic) acid (1) consists in Sonogashiry reacting 4,4'-dihalogeno-2,2'-bipyridine with ethynyltrimethylsilane in organic solvent such as aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, in the presence of a palladium catalyst selected from the group consisting of palladium(ll) dihalides, palladium(li) acetate, palladium(ll) sulf
  • Trimethylsilyl group in the intermediate are removed with the use of organic or inorganic fluorides or alkaline hydrolysis in mixture of water and alcohol or tetrahydrofuran.
  • the resulting 4,4-diethynyl ⁇ 2,2'-bipyndine without isolation is reacted with an ester of 5-hydroxy-6-halo-2-methyi-benzofuran-3- carboxy!ic acid at room temperature or higher temperature to yield the ligand of formula I, which is hydrolyzed under basic or acidic conditions, and if necessary, isolating thereof using a known method.
  • a method for obtaining of symmetrical ruthenium complexes 5, 7, 9 comprises reaction of compounds 1-3 with ruthenium(lll) chloride, or dichloro(p- cymene)ruthenium(ll) dimer and the inorganic thiocyanates in an inorganic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably in N,A/-dimethylformamtde, at room temperature or higher temperature.
  • an inorganic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lact
  • a method for the preparing asymmetric ruthenium complexes 4, 6, 8 comprise reacting of compounds 1-3 with 2,2'-bipyridine-4 ! 4'-dicarboxylic acid, ruthenium(lll) chloride, or a dimer of dichloro(p-cymene)ruthenium(l! and inorganic thiocyanates in organic solvent such as aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic ha!ohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,A/-dimethylformamide, at room temperature or higher temperature.
  • organic solvent such as aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic ha!ohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N
  • 4,4'-Dihalogeno-2,2'-bipyridine is subjected to a Sonogashira reaction with ethynyltrimethylsilane in dry toluene in the presence of [1 ,1 '-bis(diphenylphosphino)- ferrocene]dichloropailadium(ll), copper iodide, and diisopropylamine as a base, at room temperature or higher temperature. Trimethylsilyl group in the intermediate product is removed with tetrabutylammonium fluoride.
  • ligands 1-3 are reacting with a dimer of dichloro(p- cymene)ruthenium (II), with or without addition of 2,2 , -bipyrsdyl-4,4'-dicarboxy!ic acid, in the dark in ⁇ /,/V-dimethylformamide, at a temperature of 140- 50°C, and then without isolation of the ammonium thiocyanate.
  • the product is isolated using filtration, dried under reduced pressure and purified on a Sephadex LH-20, eluted with N,N- dimethylformamide.
  • ruthenium complexes are insoluble in alcohols, acetonitrile, valeronitrile and other organic solvents with the exception of /V,W-dimethylformamide and dimethyisuifoxide.
  • they are converted into tetrabutylammonium salts by titration with tetrabutylammonium hydroxide in ethanol to pH> 7, filtered and then titrated with dilute nitric acid(V) to pH 4-6, then ethanol was removed, washed with water at pH 4-6 and dried in vacuo over phosphorus pentoxide or in the air.
  • the so obtained salts are brown or black solids exhibiting absorption in the UV-Vis range both in the crystalline state and in solution.
  • the products are stable in air and after exposure to sunlight.
  • Ruthenium complexes 4-9 in form of the tetrabutylammonium salts in the ethanol solution at a concentration of 1 *10 ⁇ 4 mol/dm 3 show absorption of electromagnetic radiation in the UV-Vis range.
  • Ligand 1 according to the invention is prepared by three-step synthesis performed in a single process, without isolation of intermediates.
  • Ethynyltrimethylsilane (1.2766 g, 13 mmol) in dry toluene (5 mL) was added and heated at 80°C under a nitrogen 1.2766 atmosphere up to disappearance of etynylotrimethylsilane according to GC (2 h). After cooling to the room temperature, 1 solution of tetrabutyiammonium fluoride in dry tetrahydrofuran (13 mL) was added and stirred for 1 minute.
  • octyl 5-hydroxy-6-iodo-2-methyi- benzofuran-3-carboxylate (4.3040 g, 10 mmol) in dry toluene (50 mL) was added and stirred at 80 D C for 14 hours, it was allowed to cool to room temperature, water (40 mL) was added and the precipitate was filtered off on a Buchner funnel. The precipitate was transferred to the 250 mL flask and water (50 mL) and diethyl ether (50 mL) were added and stirred for 10 minutes. The precipitate was again filtered on a Buchner funnel and dried in vacuum over phosphorus pentoxide to yield 3.8870 g (96%) of pure product. M.p.
  • Ligand 2 according to the invention is prepared by a one-step synthesis.
  • [2,2'-Bipyridine]-4,4'- dikarboaldehyd (0.5088 g, 2.4 mmol) was added and the temperature was raised to 60°C for 5 minutes. The mixture was stirred at this temperature for 40 minutes, water (45 mL) added, filtered the resulting precipitate, which was washed with water (3x30 mL) and methanol (3 x 25 mL) and air dried to give 2.80 g of a dark orange powder. The crude product was heated in boiling p-xyiene (20 mL) containing a crystal of iodine for 1.5 hours.
  • Ligand 3 of the invention is prepared by a one-step synthesis.
  • Complex 4 according to the invention is prepared by a one-step synthesis.
  • 2,2'-Bipyridine-4,4'-dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for a further 4 hours.
  • Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and W,W-dimethylformamide removed using a rotary evaporator. To the residue water (100 mL) was added and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product.
  • the product was purified twice on Sephadex LH-20, eluted with W,W-dimethylformamide and the main band collected to yield 0.440 g (35%) of black, glossy product.
  • the complex 5 of the present invention is prepared by a one-step synthesis.
  • Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and /V,/V-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate was filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /,/V-dimethylformamide and the main band collected to yield 0.775 g (56%) of black, glossy product.
  • Complex 6 according to the invention is prepared by a one-step synthesis.
  • 2,2'-Bipyridine-4,4'- dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for 4 hours.
  • Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours.
  • Mixture was cooled to room temperature, the precipitate was filtered off and N,W-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 1 .182 g of crude product.
  • the product was purified twice on Sephadex LH-20, eluted with /V-dimethylformamide and the main band collected to yield 0.834 g (51%) of b!ack, glossy product.
  • the resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutyiammonium salt as a black powder, M.p.> 300°C.
  • Complex 7 according to the invention is prepared by a one-step synthesis.
  • Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered off. The precipitate was washed with more water (100 mL) and dried to give 1.305 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /, ⁇ -dimethylformamide and the main band collected, yielding 0.9150 g (59%) of black, glossy product.
  • Complex 8 is prepared by a one-step synthesis.
  • Dinner dichloro(p-cymene)ruihenium (il) (0.1531 g, 0.25 mmol) and ester octyl ester 2-((5H-cyclopenta[ ,2 ⁇ 0:5,4"i ']dipirydyn-5-ylidene)methyl)-6-methyibenzo[1 ,2- 0:4,5-0']difuran-3,7-dicarboxylic (0.3314 g, 0.5 mmol) in dry /V,A/-dimethylformamide (20 mL) was heated in the dark at 150°C for 2 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry.
  • the product was purified twice on Sephadex LH- 20, eiuted with N,/V-dimethylformamide and the main band collected to yield 0.206 g (37%) of black, glossy product.
  • Complex 9 according to the invention is prepared by a one-step synthesis.
  • Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.872 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /,/V-dimethyl-formamide and the main band collected, yielding 0.6237 g (57%) of black, glossy product.

Abstract

Cette invention concerne un nouveau ligand pour la synthèse de complexes de ruthénium photosensibilisants destinés à être utilisés dans des DSSC, ledit ligand comprenant dans sa structure un fragment benzodifurane lié directement ou par une liaison multiple au système 2,2'-bipyridine aux positions 4,4' ou au système fluorène et des procédés de préparation dudit ligand. L'objet de l'invention est également un nouveau complexe de ruthénium photosensibilisant symétrique ou asymétrique destiné à être utilisé dans des DSSC dérivé dudit ligand et des procédés de préparation dudit complexe. Les complexes obtenus ont des coefficients d'extinction molaire élevés dans la plage de la lumière visible et sont stables dans un environnement d'air et après exposition à la lumière du soleil, et peuvent être utilisés pour la production de cellules solaires sensibilisées à colorant (DSSC). Les procédés mis au point sont avantageux en raison de conditions de réaction douces, d'une répétabilité et modération élevées ou de rendements élevés.
PCT/PL2015/000206 2015-01-05 2015-12-23 Dérivés de benzo[1,2-b:4,5-b]furane à titre de ligands de colorants au ruthénium et procédés pour les obtenir WO2016111636A1 (fr)

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PL410875A PL238407B1 (pl) 2015-01-05 2015-01-05 Pochodne benzo[1,2-b:4,5-b’]difuranu jako związki do syntezy kompleksów rutenowych, kompleksy rutenowe zawierające pochodne benzo[1,2-b:4,5-b’]difuranu jako ligandy i sposoby ich wytwarzania
PLP.410875 2015-01-05

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Cited By (2)

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WO2018208712A1 (fr) * 2017-05-09 2018-11-15 Warner Babcock Insitute For Green Chemistry, Llc Stilbène et dérivés de stilbène fusionnés utilisés en tant que colorants de cellules solaires
WO2020014195A1 (fr) * 2018-07-10 2020-01-16 Ambient Photonics, Inc. Colorants de cellules solaires pour cellules solaires sensibilisées par colorant à base d'oxydo-réduction de cuivre et leurs combinaisons

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US11664171B2 (en) 2017-05-09 2023-05-30 Ambient Photonics, Inc. Stilbene and fused stilbene derivatives as solar cell dyes
WO2020014195A1 (fr) * 2018-07-10 2020-01-16 Ambient Photonics, Inc. Colorants de cellules solaires pour cellules solaires sensibilisées par colorant à base d'oxydo-réduction de cuivre et leurs combinaisons
US11286244B2 (en) 2018-07-10 2022-03-29 Ambient Photonics, Inc. Solar cell dyes for copper redox based dye sensitized solar cells and combinations thereof

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