WO2012175536A1 - Dyes, method of making them, and their use in dye-sensitized solar cells - Google Patents

Dyes, method of making them, and their use in dye-sensitized solar cells Download PDF

Info

Publication number
WO2012175536A1
WO2012175536A1 PCT/EP2012/061785 EP2012061785W WO2012175536A1 WO 2012175536 A1 WO2012175536 A1 WO 2012175536A1 EP 2012061785 W EP2012061785 W EP 2012061785W WO 2012175536 A1 WO2012175536 A1 WO 2012175536A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
group
groups
formula
alkyl groups
Prior art date
Application number
PCT/EP2012/061785
Other languages
French (fr)
Inventor
Mohammad Khaja Nazeeruddin
Peng Gao
Michael Graetzel
Max Josef Braun
Taichi MIYAJI
Original Assignee
Solvay Sa
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Solvay Sa filed Critical Solvay Sa
Publication of WO2012175536A1 publication Critical patent/WO2012175536A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D421/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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 relates to organic dye compounds, methods of making the same, and their use as dyes in photoelectric conversion devices, especially in dye-sensitized solar cells (DSSC).
  • DSSC dye-sensitized solar cells
  • the commercial solar cells convert light into electricity by exploiting the photovoltaic effect that exists at semiconductor junctions.
  • the commercial solar cells absorb energy from visible light and converts excited charge carriers thereof to electric energy.
  • the main commercial solar cells are silicon-based solar cells.
  • silicon-based solar cell there are shortcomings in that high energy costs for material processing is required and many problems to be addressed such as environmental burdens and cost and material supply limitations are involved.
  • amorphous silicon solar cell there are also shortcomings in that energy conversion efficiency decreases when used for a long time due to deterioration in a short period.
  • DSSC dye-sensitized solar cell
  • the DSSC offers the prospect of a cheap and versatile technology for large scale production of solar cells.
  • the dye-sensitized solar cell (DSSC) is formed by a combination of organic and inorganic components that could be produced at a low cost.
  • the dye-sensitized solar cells have advantages over silicon-based solar cells in terms of simplified processing steps, low fabrication cost, transparency and pleochroism.
  • the dye-sensitized solar cells can be fabricated from flexible substrates to function as cells of mobility and portability.
  • Dye- sensitized solar cells have also the advantage to be lightweight.
  • the dye- sensitized solar cells have lower energy (photoelectric) conversion efficiency over that of the silicon-based solar cells such that a wide range of researches are briskly under way to enhance the energy conversion efficiency.
  • Ti0 2 titanium dioxide
  • Ti0 2 titanium dioxide
  • the assembly of titanium dioxide nanoparticles is well connected to their neighbors.
  • Ti0 2 is the preferred material for the nanoparticles since its surface is highly resistant to the continued electron transfer. However, Ti0 2 only absorbs a small fraction of the solar photons (those in the UV). The dye molecules attached to the semiconductor surface are used to harvest a great portion of the solar light.
  • the dye molecules usually consist of one metal atom and a large organic structure that provides the required properties (wide absorption range, fast electron injection, and stability), such as ruthenium complexes.
  • the dye is sensible to the visible light. The light creates and excites in the dye highly energetic electron, which is rapidly injected to the semiconductor (usually Ti0 2 ) nanoparticles.
  • the nanoparticulate semiconductor functions as the transporter of light induced electrons towards the external contact, a transparent conductor that lies at the basis of the semiconductor (usually Ti0 2 ) film.
  • dye C220 comprising 4,4'-didodecyl-4H- cyclopenta[2, l-b:3,4-b']dithiophene (CPDT) segment as spacer between the donor and the acceptor groups of the sensitizer, disclosed in a publication from Cai et al. (NanoLetters, 1 1 , 1452-1456, (201 1)).
  • CPDT 4,4'-didodecyl-4H- cyclopenta[2, l-b:3,4-b']dithiophene
  • the purpose of the present invention is to provide new organic dyes showing particularly advantageous properties when used in photoelectric conversion devices, in particular in dye sensitized solar cells (DSSC), especially an improved conversion efficiency of the devices or cells. More particularly, the purpose of the present invention is to provide new dyes having a broad absorption spectrum, particularly in the visible and near-IR regions, i.e. absorbing as much of the solar spectrum as possible.
  • the new dyes of the present invention should also exhibit a high molar extinction coefficient. Such dyes should generally have an improved communication and directionality of the electrons when being transferred from the sensitizer to the semiconductor electrode.
  • Such dyes should also contribute to the long-term stability of such devices, for example, better resistance to water contained in trace amounts in the devices and better shielding of the Ti-electrode against corrosion through components present in the electrolyte, such as the triiodide/iodide couple.
  • the dyes should also be anchored and/or persistently attached to the semiconductor surface and/or to the surface of the photoelectrode. The attachment should be such that the dye stays attached over extended periods of several months and preferably years. Last, the dyes should present low aggregation state, especially low ⁇ -stacked aggregation state.
  • the present invention therefore relates to compounds of following formula :
  • n is an integer from 1 to 10
  • ⁇ and ⁇ being optional bridges electronically conjugating respectively D to B and B to A
  • the ⁇ -electron acceptor group (A) comprises at least two anchoring groups
  • n is preferably an integer from 2 to 4, especially 2.
  • n is an integer of 1.
  • n 2 and the present invention relates to compounds of general formula
  • (D) are ⁇ -electron donor groups electronically conjugated to a ⁇ -electron acceptor group (A) through ⁇ -electron bridges (B), the ⁇ and ⁇ being optional bridges electronically conjugating respectively D groups to B groups and B groups to A group, and wherein the ⁇ -electron acceptor group (A) comprises at least two anchoring groups.
  • One of the essential features of the present invention resides in the use of donor-acceptor ⁇ -conjugated dyes comprising at least two anchoring groups on the acceptor part of the molecule. Indeed, it has been surprisingly found that such dyes, based on donor-acceptor ⁇ -conjugated compounds comprising at least two anchoring groups on the acceptor moiety exhibit advantageous properties when used in photoelectric conversion devices, in particular in dye sensitized solar cells (DSSC). Especially, these compounds show high stability, as well as improved anchoring to the semiconductor surface and/or to the surface of the photoelectrode by the virtue of bianchoring groups leading to improved stability of the devices.
  • DSSC dye sensitized solar cells
  • the acceptor part of the molecule comprises at least two anchoring groups, usually 2, 3, 4, 5 or 6 anchoring groups, preferably 2, 3 or 4 anchoring groups, more preferably 2 anchoring groups.
  • the present invention relates to compounds of formula (I) :
  • - X is selected from N and C and, when X is C, both carbon atoms are
  • - Y is selected from N and C, preferably at least one of X and Y being C,
  • R 1 and R 2 are, independently of each other, selected from substituents of formula (a)
  • rhodanine-3 -acetic acid ( , deprotonated forms of the aforementioned, salts of said deprotonated forms, and chelating groups with ⁇ -conducting character, wherein R 8 is selected from the groups consisting of optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, and halogenated derivatives thereof,
  • ⁇ 3 is an optional bridge electronically conjugating the anchoring group (Anc) to the aromatic structure represented in formula (I),
  • R 3 and R 4 are, independently of each other, selected from substituents of formula (b)
  • B is a ⁇ -electron bridge group
  • D is a ⁇ -electron donor group
  • ⁇ and ⁇ are, independently of each other, optional bridges electronically conjugating respectively (D) to (B) and (B) to the aromatic structure represented in formula (I), part of acceptor group (A).
  • the ⁇ -electron acceptor group (A) includes the aromatic structure represented in formula (I) and substituents R 1 and R 2 .
  • Substituents R 3 and R 4 each include ⁇ -electron bridge group (B) and ⁇ -electron donor group (D) as well as optional bridges ⁇ 1 ⁇ ⁇ .
  • compounds of formula (I) are selected from the group consisting of following compounds (la), (lb), (Ic), (Id), (le), (If), (lg), (Ih) and (Ii) :
  • the structures as defined in formula (I) and in preferred formulas (la) to (Ii) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
  • anchoring groups may typically be selected from -COOH, -P0 3 H 2 , -P0 4 H 2 , -S0 3 H, -CONHOH, acetylacetonate, acrylic acid derivatives, malonic acid derivative, rhodanine-3 -acetic acid rotonated forms of the aforementioned, salts of said deprotonated forms, and chelating groups with ⁇ -conducting character, preferably from -COOH and acrylic acid derivatives.
  • Malonic acid derivatives suitable as anchoring groups may for example be selected from groups of
  • formula -CR 6 C(COOH) 2
  • R 6 is selected from H and optionally halogenated alkyl groups, especially from H and optionally fluorinated alkyl groups.
  • examples of the heteroatom-containing variants include thiazole moiety.
  • Preferred compounds comprising a thiophene moiety as optional bridge ⁇ 3 may for instance be selected from the group consisting of following
  • substituents R 3 and R 4 are preferably linked to the carbon atoms adjacent to group X, as illustrated in following Formula (II) :
  • ⁇ -electron bridge group (B) preferably comprises at least three electronically conjugated bonds.
  • ⁇ -electron bridge group (B) comprises at least one group selected from the following structures :
  • R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more particularly from linear C6-C12 alkyl groups and phenyl group.
  • said groups may be further substituted, especially on thiophene moieties, for instance by alkyl groups, preferably CI -CI 2 alkyl groups, more preferably C1-C6 alkyl groups, most preferably linear C1-C6 alkyl groups ; by aryl groups, preferably phenyl groups ; by alkoxy groups such as methoxy, - OC 6 Hi3 or -O-CH 2 -CH 2 -O- ; by ketones such as -COMe ; by halogen atoms such as Br, F, I and CI.
  • R can be a hydrogen or CN.
  • ⁇ - electron bridge group (B) can be selected from the group comprising at least one group selected from the following structures :
  • ⁇ -electron bridge group (B) may also comprise a porphyrine, for instance a porphyrine selected from the following structures :
  • R are independently selected from optionally branched CI -CI 8 alkyl and alkoxy groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched CI -CI 8 alkyl and alkoxy groups, for instance t-butyl, -OCsHi 7 or -O-C12H25.
  • said groups may be further substituted, by halogen atoms such as Br, F, I and CI.
  • ⁇ -electron donor group (D) can be chosen from the following structures :
  • R are independently selected from optionally branched CI -C I 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C 12 alkyl groups and phenyl group.
  • said structures may be further substituted, for instance ; by alkyl groups, preferably CI -C I 2 alkyl groups, more preferably C I -C6 alkyl groups, most preferably linear C1-C6 alkyl groups ; by aryl groups, preferably phenyl groups, including -CH 2 Ph, -CH(Ph) 2 or -C(Ph) 3 groups ; by alkoxy groups such as methoxy, or -OC 6 Hi3 ; by amino groups such as -NMe 2 , or by halogen atoms such as Br, F, I and CI.
  • alkyl groups preferably CI -C I 2 alkyl groups, more preferably C I -C6 alkyl groups, most preferably linear C1-C6 alkyl groups
  • aryl groups preferably phenyl groups, including -CH 2 Ph, -CH(Ph) 2 or -C(Ph) 3 groups
  • alkoxy groups such as methoxy, or -
  • bridges ⁇ and ⁇ electronically conjugating respectively (D) with (B) and (B) to the aromatic structure represented in formula (I), may be absent or present, independently of each other. If both bridges ⁇ and ⁇ are present, they may be the same or different.
  • heteroatom-containing variants include thiazole group.
  • both bridges ⁇ and ⁇ may be absent, (D) being directly connected with (B) and (B) being directly connected with (A).
  • both bridges ⁇ and ⁇ may be present.
  • bridge ⁇ electronically conjugating (D) with (B) may be absent and bridge ⁇ electronically conjugating (B) with (A) may be present.
  • bridge ⁇ electronically conjugating (D) with (B) may be present and bridge ⁇ electronically conjugating (B) with (A) may be absent.
  • the second and fourth specific embodiments are preferred, typically the fourth embodiment being especially preferred.
  • second specific embodiment is particularly preferred and bridge ⁇ is advantageously selected from alkyne group or combination of alkyne and/or phenyl groups, as illustrated by structures (Is) and (It) :
  • R3' and R4' corresponds to the substituent R 3 or R 4 as defined above, and rest of them is selected from the group consisting of hydrogen, halides, and the ⁇ -electron donor group (D)a.
  • the compounds of formula (III) are selected from the group consisting of following compounds (Ilia) and (Illb)
  • R 1 , R 2 , R3' and R4' have the same meaning as defined above.
  • the structures as defined in formula (III) and in preferred formulas (Ilia) and (Illb) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
  • the present invention relates to compounds of formula (IV) :
  • the compounds of formula (IV) are selected from the following compounds (IVa) and (IVb) :
  • the structures as defined in formula (IV) and in preferred formulas (IVa) and (IVb) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
  • the present invention relates to compounds of formula (V) :
  • the structures as defined in formula (V) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to compounds of formula (VI) :
  • the structures as defined in formula (VI) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to compounds of formula (VII) :
  • the structures as defined in formula (VII) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to com ounds of formula (VIII) :
  • the structures as defined in formula (VIII) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to compounds of formula (IX) :
  • the structures as defined in formula (IX) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to compounds of formula (X) :
  • the structures as defined in formula (X) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the present invention relates to compounds of formula (XI) :
  • the structures as defined in formula (XI) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
  • the compound of the present invention has structure (la) and is selected from the group consisting of :
  • R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
  • the compound of the present invention has structure (lb) and is selected from the group consisting of :
  • Compound 35 Compound 36 where R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
  • the compound of the present invention has structure (Ic) and is selected from the group consisting of :
  • R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
  • the compound of the present invention has structure (If) and is selected from the group consisting of :
  • R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
  • the compound of the present invention has structure (Ij) and is selected from the group consisting of :
  • R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
  • the compound of the present invention comprises a porphyrine as ⁇ -electron bridge group (B) and is selected from the following structures :
  • the compound of the present invention is selected from the following structures : HojtO
  • Compound 79 Any of the compounds of the present invention described herein is a dye which is suitable for use photoelectric conversion devices, especially in dye- sensitized solar cells (DSSC).
  • the present invention therefore also relates to the use of a compound of the present invention in photoelectric conversion devices, especially in DSSC.
  • the present invention also relates to the use the fluorinated compounds of the present invention in dye-sensitized solar cells (DSSC) comprising TiOF 2 (titanyl oxy fluoride, titanium oxy fluoride or titanium fluoride oxide) as semiconductor.
  • DSSC dye-sensitized solar cells
  • TiOF 2 titanium oxy fluoride or titanium fluoride oxide
  • the conduction band edge of TiOF 2 is lower in energy compared to the conduction band of Ti0 2 while the fluorinated compounds of the present invention may have a lower LUMO level compared to similar non- fluorinated compounds.
  • the photo-induced electron transfer from the excited dye to the semiconductor should be improved.
  • Such combination of fluorinated compound with TiOF 2 is thus especially advantageous.
  • the fluorinated compounds of the present invention may also be especially suitable for use in dye- sensitized solar cells (DSSC) comprising Sn0 2 as semiconductor material.
  • DSSC dye- sensitized solar cells
  • the TiOF 2 is preferably used in the form of TiOF 2 nanoparticles, in particular TiOF 2 particles having a mean primary particle size from 15 to 50 nm.
  • the layer thickness is typically from 500 nm to 10 ⁇ .
  • the TiOF 2 may be used as the sole semiconductor in the DSSC semiconductor layer or may be combined in mixture with any other suitable semiconductor compound, for instance Ti0 2 .
  • Another possibility is to have at first a dense Ti0 2 layer on the conducting glass followed by a nanoporous TiOF 2 layer.
  • the present invention further relates to a photoelectric conversion device, preferably a dye-sensitized solar cell, which comprises the compound of the present invention.
  • a photoelectric conversion device preferably a dye-sensitized solar cell
  • the compound of the present invention is used as a dye, in particular as a sensitizing dye, in such device or cell.
  • the present invention further relates to a method for making the above- mentioned compounds, in particular by transition mental catalyzed cross- coupling reaction, Knoevenagel condensation reaction, lithium-halogen exchange reaction or Friedel-Crafts reaction.
  • the compound of the present invention may be further isolated, for instance by column chromatography, preferably by high pressure liquid chromatography (HPLC).
  • HPLC high pressure liquid chromatography
  • Figure 1 shows the synthetic route to prepare Dye 1 according to Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)

Abstract

Dyes, method of making them, and their use in photoelectric conversion devices, especially in dye-sensitized solar cells. The dye compounds are organic compounds of formula (D-π1-B-π2+)n-A comprising at least one sequence D-π1-B-π2 connected to a group A, wherein D is a π-electron donor group electronically conjugated to a π-electron acceptor group (A) through a π-electron bridge group(B), n is an integer from 1 to 10, π1 and π2 being optional bridges electronically conjugating respectively D to B and B to A, and wherein the π-electron acceptor group (A) comprises at least two anchoring groups.

Description

Dyes, method of making them, and their use in dye-sensitized solar cells
This application claims priority to European application No. 11170588.5 filed on 20 Jun. 2011, the whole content of each of these applications being incorporated herein by reference for all purposes.
TECHNICAL FIELD
The present invention relates to organic dye compounds, methods of making the same, and their use as dyes in photoelectric conversion devices, especially in dye-sensitized solar cells (DSSC).
BACKGROUND OF THE INVENTION
Conventional solar cells convert light into electricity by exploiting the photovoltaic effect that exists at semiconductor junctions. In other words, the commercial solar cells absorb energy from visible light and converts excited charge carriers thereof to electric energy. At present, the main commercial solar cells are silicon-based solar cells. For a silicon-based solar cell, there are shortcomings in that high energy costs for material processing is required and many problems to be addressed such as environmental burdens and cost and material supply limitations are involved. For an amorphous silicon solar cell, there are also shortcomings in that energy conversion efficiency decreases when used for a long time due to deterioration in a short period.
Recently, many attempts have been undertaken to develop low-cost organic solar cells, whereby development of one particular type of solar cell which is a dye-sensitized solar cell (DSSC) is accelerated that is a class of molecular photovoltaic cell which is based on a semiconductor sensitized anode, a counterelectrode and an electrolyte. The sensitizer absorbs incoming light to produce excited electrons.
The DSSC offers the prospect of a cheap and versatile technology for large scale production of solar cells. The dye-sensitized solar cell (DSSC) is formed by a combination of organic and inorganic components that could be produced at a low cost. The dye-sensitized solar cells have advantages over silicon-based solar cells in terms of simplified processing steps, low fabrication cost, transparency and pleochroism. The dye-sensitized solar cells can be fabricated from flexible substrates to function as cells of mobility and portability. Dye- sensitized solar cells have also the advantage to be lightweight. The dye- sensitized solar cells have lower energy (photoelectric) conversion efficiency over that of the silicon-based solar cells such that a wide range of researches are briskly under way to enhance the energy conversion efficiency. In order to improve the energy conversion efficiency, extension of absorption spectra wavelength up to infrared regions is being waged with great concern. It is known that the energy bandgap (eV) for use in single junction solar cells must exceed 1.4 eV (electron volt).
One of the basic elements of a DSSC is generally a Ti02 (titanium dioxide) nanoparticulate structure sensitized with dye molecules to form its core of a DSSC. The assembly of titanium dioxide nanoparticles is well connected to their neighbors. Ti02 is the preferred material for the nanoparticles since its surface is highly resistant to the continued electron transfer. However, Ti02 only absorbs a small fraction of the solar photons (those in the UV). The dye molecules attached to the semiconductor surface are used to harvest a great portion of the solar light.
The dye molecules usually consist of one metal atom and a large organic structure that provides the required properties (wide absorption range, fast electron injection, and stability), such as ruthenium complexes. The dye is sensible to the visible light. The light creates and excites in the dye highly energetic electron, which is rapidly injected to the semiconductor (usually Ti02) nanoparticles. The nanoparticulate semiconductor functions as the transporter of light induced electrons towards the external contact, a transparent conductor that lies at the basis of the semiconductor (usually Ti02) film.
Meanwhile, metal- free organic sensitizers have been developed. For instance, a publication from Hagberg et al. {Journal of the American Chemical Society, 130, 6259-6266 (2008)) describes the use of organic sensitizers comprising donor, electron-conducting, and anchoring groups of 3 -(5 -(4- (diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5), 3-(5-bis(4- (diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D7), 5-(4-(bis(4- methoxyphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D9), and 3-(5- bis(4,4'-dimethoxydiphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (Dl 1) as sensitizing dyes in DSSC. Another publication from Zeng et al. {Chemistry of Materials, 22, 1915-1925 (2010)) describes the use of a dye comprising a binary π-conjugated spacer of ethylenedioxythiophene and dithienosilole (C219).
Figure imgf000004_0001
C219
Another example is given by dye C220 comprising 4,4'-didodecyl-4H- cyclopenta[2, l-b:3,4-b']dithiophene (CPDT) segment as spacer between the donor and the acceptor groups of the sensitizer, disclosed in a publication from Cai et al. (NanoLetters, 1 1 , 1452-1456, (201 1)).
Figure imgf000004_0002
C220
However, there is still a need for dyes that could lead to an improvement of DSSCs, in particular to improved conversion efficiency and stability. More particularly, there is still a need for dyes exhibiting a broad spectrum of adsorbed light (i.e. absorbing as much of the solar spectrum as possible), a high molar extinction coefficient, contributing to the long-term stability of the device and/or allowing an improved conversion efficiency.
In view of the above, the purpose of the present invention is to provide new organic dyes showing particularly advantageous properties when used in photoelectric conversion devices, in particular in dye sensitized solar cells (DSSC), especially an improved conversion efficiency of the devices or cells. More particularly, the purpose of the present invention is to provide new dyes having a broad absorption spectrum, particularly in the visible and near-IR regions, i.e. absorbing as much of the solar spectrum as possible. The new dyes of the present invention should also exhibit a high molar extinction coefficient. Such dyes should generally have an improved communication and directionality of the electrons when being transferred from the sensitizer to the semiconductor electrode. Such dyes should also contribute to the long-term stability of such devices, for example, better resistance to water contained in trace amounts in the devices and better shielding of the Ti-electrode against corrosion through components present in the electrolyte, such as the triiodide/iodide couple. The dyes should also be anchored and/or persistently attached to the semiconductor surface and/or to the surface of the photoelectrode. The attachment should be such that the dye stays attached over extended periods of several months and preferably years. Last, the dyes should present low aggregation state, especially low π-stacked aggregation state.
DESCRIPTION OF THE INVENTION
The present invention therefore relates to compounds of following formula :
Figure imgf000005_0001
comprising at least one sequence ϋ-π'-Β-π2 connected to a group A, wherein D is a π-electron donor group electronically conjugated to a π-electron acceptor group (A) through a π-electron bridge group (B), n is an integer from 1 to 10, π and π being optional bridges electronically conjugating respectively D to B and B to A, and wherein the π-electron acceptor group (A) comprises at least two anchoring groups n is preferably an integer from 2 to 4, especially 2. In particular, n is an integer of 1.
In a preferred embodiment, n is 2 and the present invention relates to compounds of general formula
(Ό-π -Β-π )2-Α
wherein (D) are π-electron donor groups electronically conjugated to a π-electron acceptor group (A) through π-electron bridges (B), the π and π being optional bridges electronically conjugating respectively D groups to B groups and B groups to A group, and wherein the π-electron acceptor group (A) comprises at least two anchoring groups.
One of the essential features of the present invention resides in the use of donor-acceptor π-conjugated dyes comprising at least two anchoring groups on the acceptor part of the molecule. Indeed, it has been surprisingly found that such dyes, based on donor-acceptor π-conjugated compounds comprising at least two anchoring groups on the acceptor moiety exhibit advantageous properties when used in photoelectric conversion devices, in particular in dye sensitized solar cells (DSSC). Especially, these compounds show high stability, as well as improved anchoring to the semiconductor surface and/or to the surface of the photoelectrode by the virtue of bianchoring groups leading to improved stability of the devices.
In the present invention, the acceptor part of the molecule comprises at least two anchoring groups, usually 2, 3, 4, 5 or 6 anchoring groups, preferably 2, 3 or 4 anchoring groups, more preferably 2 anchoring groups.
In an especially preferred embodiment, the present invention relates to compounds of formula (I) :
Figure imgf000006_0001
(I)
wherein :
- X is selected from N and C and, when X is C, both carbon atoms are
optionally joined by an additional carbon atom to form a C5 cycle which may bear the R3 and R4 substituents, optionally via the intermediate of a double bond,
- Y is selected from N and C, preferably at least one of X and Y being C,
- R1 and R2 are, independently of each other, selected from substituents of formula (a)
-7i3-Anc (a) wherein
Anc is an anchoring group selected from -COOH, -PO3H2, -PO4H2, -SO3H, - CONHOH, -NO2, -P(=0)(R8)(OH), acetylacetonate, acrylic acid derivatives, malonic acid derivative,
rhodanine-3 -acetic acid (
Figure imgf000006_0002
, deprotonated forms of the aforementioned, salts of said deprotonated forms, and chelating groups with π-conducting character, wherein R8 is selected from the groups consisting of optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, and halogenated derivatives thereof,
π3 is an optional bridge electronically conjugating the anchoring group (Anc) to the aromatic structure represented in formula (I),
- R3 and R4 are, independently of each other, selected from substituents of formula (b)
-π2-Β-π -ϋ (b) wherein
B is a π-electron bridge group,
D is a π-electron donor group,
π and π are, independently of each other, optional bridges electronically conjugating respectively (D) to (B) and (B) to the aromatic structure represented in formula (I), part of acceptor group (A).
In said preferred embodiment, the π-electron acceptor group (A) includes the aromatic structure represented in formula (I) and substituents R1 and R2.
Substituents R3 and R4 each include π-electron bridge group (B) and π-electron donor group (D) as well as optional bridges π1Άηά π .
In a still preferred embodiment, compounds of formula (I) are selected from the group consisting of following compounds (la), (lb), (Ic), (Id), (le), (If), (lg), (Ih) and (Ii) :
(la)
(lb)
Figure imgf000007_0001
(lc)
Figure imgf000008_0001
In the compounds according to the present invention, the structures as defined in formula (I) and in preferred formulas (la) to (Ii) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
In the compounds of the present invention, anchoring groups may typically be selected from -COOH, -P03H2, -P04H2, -S03H, -CONHOH, acetylacetonate, acrylic acid derivatives, malonic acid derivative, rhodanine-3 -acetic acid
Figure imgf000009_0001
rotonated forms of the aforementioned, salts of said deprotonated forms, and chelating groups with π-conducting character, preferably from -COOH and acrylic acid derivatives. Acrylic acid derivatives may for instance be selected from groups of formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3. Malonic acid derivatives suitable as anchoring groups may for example be selected from groups of
formula -CR6=C(COOH)2 where R6 is selected from H and optionally halogenated alkyl groups, especially from H and optionally fluorinated alkyl groups. Further, examples of the anchoring groups include -N02 and - P(=0)(R8)(OH) wherein R8 is selected from the groups consisting of optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more particularly from linear C6-C12 alkyl groups and phenyl group, and halogenated derivatives thereof, such as CF3.
In the present invention, if an optional bridge π3 is present, electronically conjugating the anchoring group(s) (Anc) to the aromatic structure represented in formula (I), said optional bridge may be selected from aromatic ring system, alkene group, polyene system, alkyne group, polyyne system or heteroatom- containing variants of such systems wherein one or more carbon atoms and/or one or more C=C double bonds are replaced by a heteroatom, preferably from alkene group, polyene system and thiophene moiety, more preferably from alkene group and thiophene moiety condensed to the aromatic structure represented in formula (I), most preferably from -CH=CH- group and thiophene
Figure imgf000010_0001
moieties of formula and linked to the aromatic structure represented in formula (I) through respectively positions 2 and 3 or 3 and 4 of the thiophene moiety and to Anc in position 5 of the thiophene moiety, where R7 is selected from H and alkyl groups substituted by at least one halogen atom, preferably from H, -CH2F, -CHF2, -CF3, -CF2C1 and -C2F5. Further, examples of the heteroatom-containing variants include thiazole moiety.
Preferred compounds comprising a thiophene moiety as optional bridge π3 may for instance be selected from the group consisting of following
compounds (Ik) to (Ir) :
Compound (Ij),
Compound (Ik),
Figure imgf000010_0002
Compound (Im),
Compound (In),
Compound (Io),
Compound (Ip),
Compound (Iq),
Figure imgf000011_0001
Compound (Ir).
Mixtures of the above-mentioned possibilities, thus unsymmetrical compounds, are also included in the present invention even if not explicitly designated by their formulas. In a further preferred embodiment, substituents R3 and R4 are preferably linked to the carbon atoms adjacent to group X, as illustrated in following Formula (II) :
Figure imgf000012_0001
(II)
In the present invention, π-electron bridge group (B) preferably comprises at least three electronically conjugated bonds. Advantageously, π-electron bridge group (B) comprises at least one group selected from the following structures :
Figure imgf000012_0002
Figure imgf000013_0001
where R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more particularly from linear C6-C12 alkyl groups and phenyl group. Optionally, said groups may be further substituted, especially on thiophene moieties, for instance by alkyl groups, preferably CI -CI 2 alkyl groups, more preferably C1-C6 alkyl groups, most preferably linear C1-C6 alkyl groups ; by aryl groups, preferably phenyl groups ; by alkoxy groups such as methoxy, - OC6Hi3 or -O-CH2-CH2-O- ; by ketones such as -COMe ; by halogen atoms such as Br, F, I and CI. Further, R can be a hydrogen or CN. Furthermore, π- electron bridge group (B) can be selected from the group comprising at least one group selected from the following structures :
Figure imgf000013_0002
where R has the same meaning as denoted above.
In a further embodiment of the present invention, π-electron bridge group (B) may also comprise a porphyrine, for instance a porphyrine selected from the following structures :
Figure imgf000014_0001
where R are independently selected from optionally branched CI -CI 8 alkyl and alkoxy groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched CI -CI 8 alkyl and alkoxy groups, for instance t-butyl, -OCsHi7 or -O-C12H25. Optionally, said groups may be further substituted, by halogen atoms such as Br, F, I and CI.
In the present compounds π-electron donor group (D) can be chosen from the following structures :
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000016_0001
where R are independently selected from optionally branched CI -C I 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C 12 alkyl groups and phenyl group. Optionally, said structures may be further substituted, for instance ; by alkyl groups, preferably CI -C I 2 alkyl groups, more preferably C I -C6 alkyl groups, most preferably linear C1-C6 alkyl groups ; by aryl groups, preferably phenyl groups, including -CH2Ph, -CH(Ph)2 or -C(Ph)3 groups ; by alkoxy groups such as methoxy, or -OC6Hi3 ; by amino groups such as -NMe2, or by halogen atoms such as Br, F, I and CI.
In the present invention, bridges π and π , electronically conjugating respectively (D) with (B) and (B) to the aromatic structure represented in formula (I), may be absent or present, independently of each other. If both bridges π and π are present, they may be the same or different. Said bridges π and π , if present, may typically be selected, independently of each other, from aromatic ring system, alkene group, polyene system, alkyne group, polyyne system or heteroatom-containing variants of such systems wherein one or more carbon atoms and/or one or more C=C double bonds are replaced by a heteroatom, particularly from alkene group, polyene system and phenyl moiety ; more particularly from alkyne, -(CH=CH)n- where n is an integer from 1 to 10, phenyl groups and combinations thereof ; most preferably from alkyne, -(CH=CH)n- where n is an integer from 1 to 3, phenyl groups and combinations thereof ; especially phenyl. Further, examples of the heteroatom-containing variants include thiazole group. Combination of several groups or functions may be envisaged, especially suitable combinations being for instance alkyne group and phenyl group, alkyne group and thiophene group, or -(CH=CH)n- where n is an integer from 1 to 3 and phenyl group.
In a first specific embodiment both bridges π and π may be absent, (D) being directly connected with (B) and (B) being directly connected with (A).
In a second specific embodiment, both bridges π and π may be present. In a third specific embodiment, bridge π electronically conjugating (D) with (B) may be absent and bridge π electronically conjugating (B) with (A) may be present.
In a fourth specific embodiment, bridge π electronically conjugating (D) with (B) may be present and bridge π electronically conjugating (B) with (A) may be absent.
Usually, the second and fourth specific embodiments are preferred, typically the fourth embodiment being especially preferred.
If the compound of the present invention has structure (Id), second specific embodiment is particularly preferred and bridge π is advantageously selected from alkyne group or combination of alkyne and/or phenyl groups, as illustrated by structures (Is) and (It) :
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000018_0002
(III)
wherein :
- X, Y, R1 and R2 have the same meaning as denoted above, and
one of R3' and R4' corresponds to the substituent R3 or R4 as defined above, and rest of them is selected from the group consisting of hydrogen, halides, and the π-electron donor group (D)a.
In a still another embodiment, the compounds of formula (III) are selected from the group consisting of following compounds (Ilia) and (Illb)
Figure imgf000018_0003
wherein R1, R2, R3' and R4' have the same meaning as defined above.
In the compounds according to the present invention, the structures as defined in formula (III) and in preferred formulas (Ilia) and (Illb) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
In another further embodiment, the present invention relates to compounds of formula (IV) :
Figure imgf000019_0001
the group consisting of -COOH, -P03H2, -S03H, N02, -P(=0)(R8)(OH) wherein R8 has the same meaning as denoted above, and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In a still another further embodiment, the compounds of formula (IV) are selected from the following compounds (IVa) and (IVb) :
Figure imgf000019_0002
(IVb) wherein R1, R2 and R3 have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is independently selected from the group consisting of -COOH, -P03H2, -S03H, N02, -P(=0)(R8)(OH) wherein R8 has the same meaning as denoted above, and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (IV) and in preferred formulas (IVa) and (IVb) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F and combinations thereof.
In still another further embodiment, the present invention relates to compounds of formula (V) :
Figure imgf000020_0001
derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (V) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In still another specific embodiment, the present invention relates to compounds of formula (VI) :
Figure imgf000021_0001
(VI)
wherein :
- R1, R2, R3 and R4 have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (VI) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In another specific further embodiment, the present invention relates to compounds of formula (VII) :
Figure imgf000021_0002
(VII)
wherein :
- R1, R2 and R3 have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (VII) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In still another specific further embodiment, the present invention relates to com ounds of formula (VIII) :
Figure imgf000022_0001
(VIII)
wherein :
- R1, R2, R3 and R4 have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (VIII) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In more specific further embodiment, the present invention relates to compounds of formula (IX) :
Figure imgf000022_0002
(IX)
wherein :
- R1, R2 and R3 have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (IX) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In still more specific further embodiment, the present invention relates to compounds of formula (X) :
Figure imgf000023_0001
the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (X) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
In still further more specific embodiment, the present invention relates to compounds of formula (XI) :
R1
Figure imgf000023_0002
(XI)
wherein :
- R1, R2, R3 and R have the same meaning as denoted above, and preferably, the anchoring group for R1 and R2 is selected from -COOH and acrylic acid derivatives, such as the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
In the compounds according to the present invention, the structures as defined in formula (XI) may be further substituted, for instance with alkyl groups, aryl groups, halogenated alkyl or aryl groups, halogenated atoms, CN and combinations thereof, preferably alkyl groups, aryl groups, fluorinated alkyl or aryl groups, F, CN and combinations thereof.
Mixtures of the above-mentioned possibilities, thus unsymmetrical compounds, are also included in the present invention even if not explicitly designated by their formulas.
In a particular embodiment, the compound of the present invention has structure (la) and is selected from the group consisting of :
Figure imgf000024_0001
Compound 1 Compound 2
Figure imgf000025_0001
Compound 6 Compound 7
Figure imgf000026_0001
Compound 8 Compound 9
Figure imgf000026_0002
Compound 10
Figure imgf000026_0003
Compound 11 Compound 12
Figure imgf000027_0001
Compound 14
Figure imgf000028_0001
Compound 16
Figure imgf000029_0001
Compound 17
Figure imgf000029_0002
Compound 18
Figure imgf000030_0001
Compound 20
Figure imgf000031_0001
Compound 22
Figure imgf000032_0001
Compound 24
where R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
In another particular embodiment, the compound of the present invention has structure (lb) and is selected from the group consisting of :
Figure imgf000033_0001
Compound 25 Compound 26
Figure imgf000033_0002
Compound 27 Compound 28
Figure imgf000033_0003
Compound 29 Compound 30
Figure imgf000034_0001
Compound 31
Figure imgf000034_0002
Compound 33 Compound 34
Figure imgf000034_0003
Compound 35 Compound 36 where R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
In a further particular embodiment, the compound of the present invention has structure (Ic) and is selected from the group consisting of :
Figure imgf000035_0001
Compound 37 Compound 38
Figure imgf000035_0002
Compound 39 Compound 40
Figure imgf000035_0003
Compound 41 Compound 42
Figure imgf000036_0001
Compound 43 Compound 44 where R are independently selected from optionally branched CI -CI 8 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
In a still further particular embodiment, the compound of the present invention has structure (If) and is selected from the group consisting of :
Figure imgf000036_0002
Compound 45 Compound 46
Figure imgf000037_0001
Compound 47
Figure imgf000037_0002
Figure imgf000038_0001
Compound 50
where R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
In an additional particular embodiment, the compound of the present invention has structure (Ij) and is selected from the group consisting of :
Figure imgf000039_0001
Compound 53 Compound 54
Figure imgf000040_0001
where R are independently selected from optionally branched C 1 -C 18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group. In a last particular embodiment, the compound of the present invention comprises a porphyrine as π-electron bridge group (B) and is selected from the following structures :
Figure imgf000041_0001
Compound 58
Figure imgf000042_0001
5 Compound 60
Figure imgf000043_0001
5 Compound 62
Figure imgf000044_0001
Compound 63
Figure imgf000044_0002
Figure imgf000045_0001
Compound 65
Figure imgf000045_0002
Compound 66
In an additional particular embodiment, the compound of the present invention is selected from the following structures :
Figure imgf000046_0001
HojtO
Compound 67 Compound 68
Figure imgf000046_0002
Compound 69 Compound 70
Figure imgf000046_0003
Compound 73 Compound 74
Figure imgf000047_0001
Compound 75 Compound 76
Figure imgf000047_0002
Compound 79 Any of the compounds of the present invention described herein is a dye which is suitable for use photoelectric conversion devices, especially in dye- sensitized solar cells (DSSC). The present invention therefore also relates to the use of a compound of the present invention in photoelectric conversion devices, especially in DSSC.
The present invention also relates to the use the fluorinated compounds of the present invention in dye-sensitized solar cells (DSSC) comprising TiOF2 (titanyl oxy fluoride, titanium oxy fluoride or titanium fluoride oxide) as semiconductor. Indeed, without being bound by any theory, it is believed that the conduction band edge of TiOF2 is lower in energy compared to the conduction band of Ti02 while the fluorinated compounds of the present invention may have a lower LUMO level compared to similar non- fluorinated compounds. Furthermore, due to the lower energy level of TiOF2 conduction band compared to Ti02, the photo-induced electron transfer from the excited dye to the semiconductor should be improved. Such combination of fluorinated compound with TiOF2 is thus especially advantageous.
The fluorinated compounds of the present invention may also be especially suitable for use in dye- sensitized solar cells (DSSC) comprising Sn02 as semiconductor material.
The TiOF2 is preferably used in the form of TiOF2 nanoparticles, in particular TiOF2 particles having a mean primary particle size from 15 to 50 nm. The layer thickness is typically from 500 nm to 10 μιη. The TiOF2 may be used as the sole semiconductor in the DSSC semiconductor layer or may be combined in mixture with any other suitable semiconductor compound, for instance Ti02. Another possibility is to have at first a dense Ti02 layer on the conducting glass followed by a nanoporous TiOF2 layer.
The present invention further relates to a photoelectric conversion device, preferably a dye-sensitized solar cell, which comprises the compound of the present invention. The compound of the present invention is used as a dye, in particular as a sensitizing dye, in such device or cell.
The present invention further relates to a method for making the above- mentioned compounds, in particular by transition mental catalyzed cross- coupling reaction, Knoevenagel condensation reaction, lithium-halogen exchange reaction or Friedel-Crafts reaction.
The compound of the present invention may be further isolated, for instance by column chromatography, preferably by high pressure liquid chromatography (HPLC).
While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of systems and methods are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
Brief Description of the Drawing
Figure 1 shows the synthetic route to prepare Dye 1 according to Example 1.
Examples
Example 1 : Synthesis of Dye 1
Figure imgf000049_0001
Dye l
Synthetic scheme and yields are summarized in Figure 1.
Synthesis of tributyl(4,4-dihexyl-4H-cyclopenta[l,2-b:5,4-b']dithiophen-2- yPstannane (2)
Figure imgf000049_0002
4,4-dihexyl-4H-cyclopenta[l,2-b:5,4-b']dithiophene (215 mg, 0.53 mmol) was dissolved in THF (2 mL). At -78 °C, n-Butyllithium (0.215 mL, 2.5 M,
0.54 mmol) was added and the mixture was stirred at -78°C for 2 h. Tributyltin chloride (0.145 mL, 0.53 mmol) was added and the mixture was stirred for 16 h, while warming to room temperature. Diethyl ether (15 mL) was added and the mixture was washed with water (3-5 mL), dried with MgS04 and the solvent was evaporated. Yield: 369 mg (> 99 %).
1H-NMR (400 MHz) : π 7.05 (d, J= 4.8 Hz, 1H, Ar-H), 6.93-6.88 (m, 2H, Ar-H), 1.90-1.82 (m, 4H, -CH2CH(C2H5)(C4H9)), 1.63-1.52 (m,
6H, -CH2C3H7), 1.40-1.30 (m, 6H, -CH2CH2C2H5), 1.13-1.06 (m,
6p, -C2H4CH2CH3), 1.06-0.82 (m, 27H, alkyl-H), 0.75 (t, J= 6.7 Hz,
6H, -CH3), 058 (t, J= 7.6 Hz, 6H, -CH3).
Synthesis ofN,N-Bis(4-hexyloxyphenyl)-4-bromophenylamine (3)
Figure imgf000050_0001
To a 250 mL round-bottomed flask equipped with a magnetic stirrer and a Dean-Stark trap under reflux condenser were added 4-bromoaniline (3.4 g, 20 mmol), l-iodo-4-hexyloxybenene (16.6 g, 50.0 mmol), cuprous iodide (0.38 g, 2.0 mmol), 1,10- phenanthroline (0.40 g, 2.0 mmol), potassium hydroxide flakes (18 g, 0.32 mol), and toluene (40 mL). The reaction mixture was rapidly heated over a period of 30 min to 125 °C and maintained at this temperature for 24 h. After cooling, the mixture was diluted with dichloromethane and washed with 1 N HC1 and brine before being dried over MgS04. The crude product was purified by column chromatography (silica gel, dichloromethane/petroleum ether) 1/10) to give product (3) (8.1 g, 70%) as colorless oil.
1H NMR (300 MHz, CDC13)□ (ppm) : 7.26 (d, 2H, J = 8.9 Hz), 7.05 (d, 4H, J = 8.9 Hz), 6.87-6.80 (m, 6H), 3.96 (t, 4H, J = 6.5 Hz), 1.86-1.77 (m, 4H), 1.51-1.33 (m, 20H), 0.93 (t, 6H, J = 5.1 Hz). Synthesis of 4-(4,4-dihexyl-4H-cyclopenta[l,2-b:5,4-b,]dithiophen-2-yl)-N,N- bis(4-(hexyloxy)phenyl)-aniline (4)
Figure imgf000051_0001
4-bromo-N,N-bis(4-(hexyloxy)phenyl)aniline (3) (0.900g, 2.5mmol) was added to a solution of (2) (1.82 g, 5.5mmol) in anhydrous DMF (20mL), and the resulting mixture was purged with Ar for 30min. Pd(PPh3)4 (87mg, 0.075mmol) was then added, and the reaction mixture was heated to 80°C overnight. Excess DMF was removed under high vacuum,and the residuewas dissolved in ethyl acetate and treated with 10% aqueous KF. The mixture was filtered through a pad of Celite. The filtrate was dried over Mg2S04, filtered, and the solvent removed in vacuo. The crude product was purified by flash chromatography (silica gel, eluent : hexane/CH2Cl2 = 5: 1) to afford 1.16 g (87%) of (4) as red oil.
1H NMR(400 MHz,CD2Cl2) : π (ppm) 1.05 (t,6H), 1.50 (m, 12H), 1.86 (m, 4H), 3.99 (t, 4H), 6.78-6.86 (m, 8H), 6.87-6.92 (m, 8H), 7.0-7.04 (d, 1H), 7.05-7.07 (d, 2H).
Synthesis of dimethyl 6,6'-dichloro-2,2'-bipyridine-4,4,-dicarboxylate (6)
Figure imgf000051_0002
To a solution of dimethyl-2,2'-bipyridine-4,4'-dicarboxylate (20 g, 73.5 mmol) in acetic acid (125 ml) 80 ml of H202 (36v/v) were added. The reaction mixture was stirred and heated under reflux for 4 hours, then other 80 ml of H202 (36v/v) were carefully added and the reaction kept in reflux for 3 hours. After cooling the precipitate was collected by filtration and washed with methanol and water until all the residual acetic acid was eliminate to give 1 as pure product. The liquid was concentrated and a new crystallisation of pure product was induced. Yield : 90% (20 grams).
The next step was performed in a well dried round bottom flask equipped with a reflux condenser in nitrogen atmosphere. To a 20 g (65.8 mmol) of 1, 80 ml of POCI3 freshly distilled were carefully added. The reaction mixture was heated under reflux for 5-6 hours. After a slow cooling the product directly crystallized. The solid was collected by filtration and the excess of POCI3 was removed by distillation. The crude product was washed with a saturated aqueous solution of Na2C03, giving the title compound 6 as an off white solid (23 g, >90 %).
Synthesis of compound (5)
Figure imgf000052_0001
The reaction was performed following a similar procedure as synthesizing compound (2). Yield : 1.2 g (> 99 %). Used without purification.
Synthesis of compound (7)
Figure imgf000052_0002
Yield : 80 mg (35 %). Ή-NMR (400 MHz) : d 8.77 (s, 2H), 8.09 (s, 2H), 7.60 (s, 2H), 7.48-7.51 (d, 6H), 7.20 (s, 2H), 7.09-7.11 (d, 10H), 6.95-6.97 (d, 4H), 6.88-6.90 (d, 10H), 4.07 (s, 6H). 3.93-3.96 (t, J= 7.6 Hz, 8H). 2.04-1.82 (m, 4H), 1.63-1.52 (m, 6H), 1.40-1.30 (m, 6H), 1.13-1.06 (m, 6H), 1.06-0.82 (m, 27H), 0.75 (t, J= 6.7 Hz), 0.58 (t, J= 7.6 Hz, 12H).
Synthesis of Dye 1
Figure imgf000053_0001
To a solution of (7) (60 mg, 0.032 mmol) in THF (10 mL) was added a solution of NaOH (194 mg, 5.0 mmol) in H20 (5 mL). The reaction mixture was refiuxed for 24 h. After cooling to room temperature, the reaction mixture was treated with 1 M HCl aqueous solution and passed through the filter paper. The filtrate was washed with water to give a crude product. Purification by column chromatography on silica gel (CH2Cl2:MeOH = 10: 1) gave Dye 1 (42 mg, 72 %) as a red solid.
1H-NMR (400 MHz) : d 8.89 (s, 2H), 8.34 (s, 2H), 7.83 (s, 2H), 7.45-7.47
(d, 6H), 7.26 (s, 2H), 7.01-7.06 (m, 10H), 6.89-6.91 (d, 6H), 6.82-6.86 (m, 10H), 3.93-3.96 (t, J= 7.6 Hz, 8H), 2.04-1.82 (m, 4H), 1.63-1.52 (m, 6H), 1.40-1.30 (m, 6H), 1.13-1.06 (m, 6H), 1.06-0.82 (m, 27H), 0.75 (t, J= 6.7 Hz), 0.58 (t, J= 7.6 Hz, 12H).

Claims

C L A I M S
1. A compound of formula
Figure imgf000054_0001
comprising at least one sequence ϋ-π'-Β-π2 connected to a group A, wherein D is a π-electron donor group electronically conjugated to a π-electron acceptor group (A) through a π-electron bridge group (B), n is an integer from 1 to 10, π and π being optional bridges electronically conjugating respectively D to B and B to A, and wherein the π-electron acceptor group (A) comprises at least two anchoring groups.
2. The compound of claim 1, wherein n is 2.
3. The compound of claim 1 or 2, having anyone of the following formula (I) to formula (XI) :
Figure imgf000054_0002
(I)
Figure imgf000054_0003
(Π)
Figure imgf000054_0004
Figure imgf000055_0001
Figure imgf000055_0002
Figure imgf000055_0003
Figure imgf000055_0004
Figure imgf000055_0005
(VIII)
Figure imgf000056_0001
(IX)
Figure imgf000056_0002
(X)
Figure imgf000056_0003
(XI)
wherein
- X is selected from N and C and, when X is C, both carbon atoms are
optionally joined by an additional carbon atom to form a C5 cycle which may bear the R3 and R4 substituents, optionally via the intermediate of a double bond,
- Y is selected from N and C, preferably at least one of X and Y being C,
- R1 and R2 are, independently of each other, selected from substituents of formula (a)
-7i3-Anc (a) wherein Anc is an anchoring group selected
from -COOH, -P03H2, -P04H2, -S03H, -CONHOH, N02, -P(=0)(R acetylacetonate, acrylic acid derivatives, malonic acid derivative, -
COOH
rhodanine-3 -acetic acid (
Figure imgf000057_0001
), deprotonated forms of the aforementioned, salts of said deprotonated forms, and chelating groups with π-conducting character, preferably from -COOH and acrylic acid derivatives, wherein R8 is selected from the groups consisting of optionally branched Cl- C18 alkyl groups and optionally substituted C5-C12 aryl groups, and halogenated derivatives thereof, π3 is an optional bridge electronically conjugating the anchoring group (Anc) to the aromatic structure represented in formula (I),
R3 and R4 are, independently of each other, selected from substituents of formula (b)
-π2-Β-π -ϋ (b) wherein
B is a π-electron bridge group, D is a π-electron donor group, π and π are, independently of each other, optional bridges electronically conjugating respectively (D) to (B) and (B) to the aromatic structure represented in formula (I), which is part of acceptor group (A).
4. The compound of anyone of the preceding claims, selected from compounds (la), (lb), (Ic), (Id), (le), (If), (lg), (Ih), (Ii), (Ilia), (Illb), (IVa) and (IVb) :
Figure imgf000057_0002
(la)
Figure imgf000058_0001
Figure imgf000059_0001
5. The compound of anyone of the preceding claims, wherein acrylic acid derivatives have the formula -CH=C(R5)-COOH where R5 is selected from H, CN and alkyl groups substituted by at least one halogen atom, preferably from H, CN and CF3.
6. The compound of anyone of the preceding claims, comprising no optional bridge π3.
7. The compound of anyone of the preceding claims, wherein an optional bridge π3 is present and is selected from aromatic ring system, alkene group, polyene system, alkyne group, polyyne system or heteroatom-containing variants of such systems wherein one or more carbon atoms and/or one or more C=C double bonds are replaced by a heteroatom, preferably from alkene group, polyene system and thiophene moiety, more preferably from alkene group and thiophene moiety condensed to the aromatic structure represented in formula (I), most preferably from -CH=CH- group and thiophene moieties of formula
Figure imgf000060_0001
linked to the aromatic structure represented in formula (I) through respectively positions 2 and 3 or 3 and 4 of the thiophene moiety and to Anc in position 5 of the thiophene moiety, where R7 is selected from H and alkyl groups substituted by at least one halogen atom, preferably from H, -CH2F, -CHF2, -CF3, -CF2C1 and -C2F5.
8. The compound of anyone of the preceding claims, wherein π-electron bridge group (B) comprises at least three electronically conjugated bonds, preferably wherein (B) comprises at least one group selected from the following structures :
Figure imgf000061_0001
Figure imgf000062_0001
where R are independently selected from hydrogen, CN, optionally branched Cl- C18 alkyl groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more particularly from linear C6-C12 alkyl groups and phenyl group.
9. The compound of anyone of claim 1 to 7, wherein π-electron bridge group (B) comprises a porphyrine selected from the group consisting of:
Figure imgf000062_0002
where R are independently selected from hydrogen, CN, optionally branched Cl- C18 alkyl and alkoxy groups and optionally substituted C5-C12 aryl groups, particularly from optionally branched CI -CI 8 alkyl and alkoxy groups, especially t-butyl, -OCsHn and -O-C12H25.
10. The compound of anyone of the preceding claims, wherein π-electron donor group (D) is selected from the group consisting of :
Figure imgf000063_0001
Figure imgf000064_0001
where R are independently selected from hydrogen, CN, optionally branched Cl- C18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
1 1. The compound of anyone of the preceding claims, wherein both bridges π and π are absent.
12. The compound of anyone of the preceding claims, wherein at least one of bridges π and π is present, preferably bridge π , and are selected, independently of each other, from aromatic ring system, alkene group, polyene system, alkyne group, polyyne system or heteroatom-containing variants of such systems wherein one or more carbon atoms and/or one or more C=C double bonds are replaced by a heteroatom, particularly from alkene group, polyene system and phenyl moiety, more particularly from alkyne, -(CH=CH)n- where n is an integer from 1 to 10, phenyl groups and combinations thereof ; most preferably from alkyne, -(CH=CH)n- where n is an integer from 1 to 3, phenyl groups and combinations thereof, especially phenyl.
13. The compound of anyone of the preceding claims, wherein the compound is selected from the group consisting of :
Figure imgf000065_0001
Compound 1 Compound 2
Figure imgf000066_0001
Figure imgf000066_0002
5 Compound 4 Compound 5
Figure imgf000067_0001
Figure imgf000067_0002
Compound 8 Compound 9
Figure imgf000067_0003
Compound 10
Figure imgf000068_0001
Compound 13
Figure imgf000069_0001
Compound 14
Figure imgf000069_0002
Compound 15
Figure imgf000070_0001
Compound 16
Figure imgf000070_0002
Compound 17
Figure imgf000071_0001
Compound 19
Figure imgf000072_0001
Compound 20
Figure imgf000072_0002
Compound 21
Figure imgf000073_0001
Figure imgf000073_0002
Compound 23
Figure imgf000074_0001
Figure imgf000074_0002
Compound 25 Compound 26
Figure imgf000074_0003
Compound 27 Compound 28
Figure imgf000075_0001
Compound 29 Compound 30
Figure imgf000075_0002
Compound 31 Compound 32
Figure imgf000075_0003
Compound 33 Compound 34
Figure imgf000076_0001
Compound 35 Compound 36
Figure imgf000076_0002
Compound 37 Compound 38
Figure imgf000076_0003
Compound 39 Compound 40
Figure imgf000077_0001
Compound 41 Compound 42
Figure imgf000077_0002
Compound 43 Compound 44
Figure imgf000077_0003
Compound 45 Compound 46
Figure imgf000078_0001
Compound 47
Figure imgf000078_0002
Figure imgf000079_0001
Compound 49
Figure imgf000079_0002
Compound 50
Figure imgf000080_0001
Compound 53 Compound 54
Figure imgf000081_0001
Compound 55
Figure imgf000081_0002
Compound 56
Figure imgf000082_0001
Compound 57
Figure imgf000082_0002
Figure imgf000083_0001
Figure imgf000083_0002
5 Compound 60
Figure imgf000084_0001
Figure imgf000084_0002
5 Compound 62
Figure imgf000085_0001
Compound 63
Figure imgf000085_0002
- 85 -
Figure imgf000086_0001
Figure imgf000086_0002
Figure imgf000087_0001
HojtO
Compound 67 Compound 68
Figure imgf000087_0002
Compound 69 Compound 70
Figure imgf000087_0003
Compound 73 Compound 74
Figure imgf000088_0001
Compound 75 Compound 76
Figure imgf000088_0002
Compound 77 Compound 78
Figure imgf000088_0003
Compound 79 where R are independently selected from hydrogen, CN, optionally branched Cl- C18 alkyl groups and optionally substituted C5-C12 aryl groups, preferably from optionally branched C6-C12 alkyl groups and optionally substituted C6 aryl groups, more preferably from linear C6-C12 alkyl groups and phenyl group.
14. The compound of anyone of the preceding claims, being a dye suitable for use in photoelectric conversion devices, in particular in dye-sensitized solar cell.
15. A dye-sensitized solar cell comprising the compound of anyone of claims 1 to 14 as a dye.
PCT/EP2012/061785 2011-06-20 2012-06-20 Dyes, method of making them, and their use in dye-sensitized solar cells WO2012175536A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11170588 2011-06-20
EP11170588.5 2011-06-20

Publications (1)

Publication Number Publication Date
WO2012175536A1 true WO2012175536A1 (en) 2012-12-27

Family

ID=44351381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/061785 WO2012175536A1 (en) 2011-06-20 2012-06-20 Dyes, method of making them, and their use in dye-sensitized solar cells

Country Status (1)

Country Link
WO (1) WO2012175536A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2765132A1 (en) * 2013-02-08 2014-08-13 Solvay SA Dye compounds, and their use in dye-sensitized solar cells
WO2014196659A1 (en) * 2013-06-06 2014-12-11 Ricoh Company, Ltd. Photoelectric conversion element and solar cell
JP2015065118A (en) * 2013-09-26 2015-04-09 株式会社リコー Photoelectric conversion element
JP2015065112A (en) * 2013-09-26 2015-04-09 株式会社リコー Photoelectric conversion element
WO2015087837A1 (en) * 2013-12-09 2015-06-18 独立行政法人産業技術総合研究所 Organic dye compound having triphenylamine with bulky substituent as electron-donating group, semiconductor thin film electrode using same, photoelectric conversion element, and photoelectrochemical solar cell
US9080055B2 (en) 2011-01-14 2015-07-14 Solvay Sa Photoelectric conversion device using TiOF2 as semiconductor
WO2019085686A1 (en) * 2017-11-02 2019-05-09 广东阿格蕾雅光电材料有限公司 Organic electroluminescent device containing carbazole and pyridine construction unit materials
CN109748913A (en) * 2017-11-02 2019-05-14 广东阿格蕾雅光电材料有限公司 Electroluminescent material based on carbazole and pyridine construction unit
CN109836430A (en) * 2019-04-11 2019-06-04 南开大学 Double triphenylamine-porphyrin-benzoic acid dyestuffs and its application in dye-sensitized solar cells
CN111349104A (en) * 2020-03-13 2020-06-30 东华大学 Organic small-molecule semiconductor material containing rhodanine fused (analogous) isatin and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1117058A1 (en) 1999-12-14 2001-07-18 Ncr International Inc. System and methods for exemplar based bar code error detection and correction
US20070017569A1 (en) * 2005-07-25 2007-01-25 General Electric Company Metal complex compositions and use thereof in dye sensitized solar cells
US20090209762A1 (en) * 2008-02-19 2009-08-20 National Central University Photosensitizer dye
WO2011039715A1 (en) * 2009-09-29 2011-04-07 Ecole Polytechnique Federale De Lausanne (Epfl) Novel ligands for sensitizing dyes of dye-sensitized solar cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1117058A1 (en) 1999-12-14 2001-07-18 Ncr International Inc. System and methods for exemplar based bar code error detection and correction
US20070017569A1 (en) * 2005-07-25 2007-01-25 General Electric Company Metal complex compositions and use thereof in dye sensitized solar cells
US20090209762A1 (en) * 2008-02-19 2009-08-20 National Central University Photosensitizer dye
WO2011039715A1 (en) * 2009-09-29 2011-04-07 Ecole Polytechnique Federale De Lausanne (Epfl) Novel ligands for sensitizing dyes of dye-sensitized solar cells

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BÉATRICE ALPHA, ELKE ANKLAM, ROBERT DESCHENAUX, JEAN-MARIE LEHN, MAREK PIETRASKIEWIEZ: "Synthesis and Characterisation of the Sodium and Lithium Cryptates of Macrobicyclic Ligands incorporating pyridine, bipyridine, and biisoquinoline units", HELVETICA CHIMICA ACTA, vol. 71, 1988, pages 1042 - 1052, XP002656808, DOI: 10.1002/hlca.19880710515 *
CAI ET AL., NANOLETTERS, vol. 11, 2011, pages 1452 - 1456
EDWIN C. CONSTABLE, MICHAEL J. HANNON, PETER HARVERSON, MARKUS NEUBURGER, ET AL: "Synthesis and coordination chemistry of 4,4-disubstituted 2,2:6,2:6,2-quaterpyridines and crystal and molecular structures of nickel(II) and cobalt(II) complexes", POLYHEDRON, vol. 19, no. 1, 2000, pages 23 - 34, XP002656807 *
GUNTHER R. PABST, OLIVER C. PFÜLLER, JÜRGEN SAUER: "The new and simple LEGO system: Synthesis and reactions of thienyl-substituted 4-tributylstannyl-2,6-oligopyridines", TETRAHEDRON, vol. 55, no. 16, 1999, pages 5047 - 5066, XP002656806 *
HAGBERG ET AL., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 130, 2008, pages 6259 - 6266
OLIVIER MAURY, LYDIE VIAU, KATELL SÉNÉCHAL, BRIGITTE CORRE, JEAN-PAUL GUÉGAN ET AL: "Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes", CHEMISTRY--A EUROPEAN JOURNAL, vol. 10, no. 18, 2004, pages 4454 - 4466, XP002656809, DOI: 10.1002/chem.200400012 *
ZENG ET AL., CHEMISTRY OFMATERIALS, vol. 22, 2010, pages 1915 - 1925

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9080055B2 (en) 2011-01-14 2015-07-14 Solvay Sa Photoelectric conversion device using TiOF2 as semiconductor
EP2765132A1 (en) * 2013-02-08 2014-08-13 Solvay SA Dye compounds, and their use in dye-sensitized solar cells
WO2014196659A1 (en) * 2013-06-06 2014-12-11 Ricoh Company, Ltd. Photoelectric conversion element and solar cell
JP2015015454A (en) * 2013-06-06 2015-01-22 株式会社リコー Photoelectric conversion element and solar cell
US9640330B2 (en) 2013-06-06 2017-05-02 Ricoh Company, Ltd. Photoelectric conversion element and solar cell
JP2015065118A (en) * 2013-09-26 2015-04-09 株式会社リコー Photoelectric conversion element
JP2015065112A (en) * 2013-09-26 2015-04-09 株式会社リコー Photoelectric conversion element
WO2015087837A1 (en) * 2013-12-09 2015-06-18 独立行政法人産業技術総合研究所 Organic dye compound having triphenylamine with bulky substituent as electron-donating group, semiconductor thin film electrode using same, photoelectric conversion element, and photoelectrochemical solar cell
JPWO2015087837A1 (en) * 2013-12-09 2017-03-16 国立研究開発法人産業技術総合研究所 Organic Dye Compound Using Triphenylamine with Bulky Substituent as Electron Donating Group, Semiconductor Thin Film Electrode, Photoelectric Conversion Device, and Photoelectrochemical Solar Cell Using the Same
WO2019085686A1 (en) * 2017-11-02 2019-05-09 广东阿格蕾雅光电材料有限公司 Organic electroluminescent device containing carbazole and pyridine construction unit materials
CN109748913A (en) * 2017-11-02 2019-05-14 广东阿格蕾雅光电材料有限公司 Electroluminescent material based on carbazole and pyridine construction unit
CN109748913B (en) * 2017-11-02 2021-05-11 广东阿格蕾雅光电材料有限公司 Electroluminescent material based on carbazole and pyridine building units
CN109836430A (en) * 2019-04-11 2019-06-04 南开大学 Double triphenylamine-porphyrin-benzoic acid dyestuffs and its application in dye-sensitized solar cells
CN111349104A (en) * 2020-03-13 2020-06-30 东华大学 Organic small-molecule semiconductor material containing rhodanine fused (analogous) isatin and preparation method and application thereof
CN111349104B (en) * 2020-03-13 2021-08-10 东华大学 Organic small-molecule semiconductor material containing rhodanine fused isatin and preparation method and application thereof

Similar Documents

Publication Publication Date Title
WO2012175536A1 (en) Dyes, method of making them, and their use in dye-sensitized solar cells
KR101018734B1 (en) Photosensitizer dye
US9716240B2 (en) High molecular extinction coefficient metal dyes
Tian et al. Low-cost dyes based on methylthiophene for high-performance dye-sensitized solar cells
Wang et al. Influence of the terminal electron donor in D–D–π–A phenothiazine dyes for dye-sensitized solar cells
US20110265876A1 (en) Novel anchoring ligands for sensitizers of dye-sensitized photovoltaic devices
WO2015161989A1 (en) Hole-transport materials for organic solar cells or organic optical sensors
US9812658B2 (en) Porphyrin based sensitizer for dye-sensitized solar cell
WO2016066494A1 (en) Hole-transport materials for organic solar cells or organic optical sensors
Duan et al. New organic dyes containing tert-Butyl-capped N-Arylcarbazole moiety for Dye-sensitized solar cells
US20140020761A1 (en) Organic dye material and dye-sensitized solar cell using same
JP5757609B2 (en) Donor-π-acceptor compound, fluorescent dye compound, and fluorescent dye compound for dye-sensitized solar cell
JP5531241B2 (en) Fullerene derivatives, semiconductor materials, photoelectric conversion elements and solar cells
JP2014527086A (en) Organic dye, dye-sensitized metal oxide semiconductor electrode, and dye-sensitized solar cell
US20140202537A1 (en) Dye-sensitized solar cell and sensitizing dye
JP5776099B2 (en) Transition metal complex, photosensitizing dye, oxide semiconductor electrode containing the dye, and dye-sensitized solar cell
US8846905B2 (en) Porphyrin complex and use thereof
Zhu et al. Asymmetrical planar acridine-based hole-transporting materials for highly efficient perovskite solar cells
JP5730031B2 (en) Fullerene derivative and photoelectric conversion element using the same
JP2018127425A (en) New squarylium derivative and organic thin film solar cell using the same
CN109096163B (en) Organic molecular material, synthesis method thereof and application of organic molecular material as hole transport layer
JP5875988B2 (en) Novel organic dye and method for producing the same
WO2014136915A1 (en) Organic dye material and dye-sensitized solar cell using same
TW201313724A (en) Dyes, method of making them, and their use in dye-sensitized solar cells
CN113801115B (en) Condensed ring imide hole transport material, preparation method thereof and perovskite solar cell application

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12728563

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12728563

Country of ref document: EP

Kind code of ref document: A1