EP3174850A1 - Neuartige synthone zur entwicklung organischer halbleiter - Google Patents

Neuartige synthone zur entwicklung organischer halbleiter

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Publication number
EP3174850A1
EP3174850A1 EP15749754.6A EP15749754A EP3174850A1 EP 3174850 A1 EP3174850 A1 EP 3174850A1 EP 15749754 A EP15749754 A EP 15749754A EP 3174850 A1 EP3174850 A1 EP 3174850A1
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Prior art keywords
groups
group
branched
straight
unsaturated
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EP15749754.6A
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English (en)
French (fr)
Inventor
Martial DEGBIA
Bruno SCHMALTZ
François TRAN-VAN
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Universite de Tours
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Universite Francois Rabelais de Tours
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    • 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
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • 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
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic 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
    • H10K85/631—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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to novel synthons, to a process for their preparation and to their use in the preparation of various materials, in particular organic semiconductors and dyes.
  • Dye-sensitized solar cells are a promising photovoltaic technology for the production of renewable and low-cost energy. These cells consist of a nanocrystalline oxide with a large energy gap, for example TiO 2 deposited on a transparent conductive oxide glass support. Molecular sensitizers, bonded through wide-gap oxide anchoring groups, inject electrons into the conduction band of the semiconductor under solar exposure. Usually, a liquid electrolyte comprising a redox system provides regeneration of the photoexcited dye.
  • liquid electrolyte based DSSCs achieve conversion efficiencies of more than 12%. However, they can cause problems of leakage and corrosion of the electrodes.
  • ssDSSC solid state DSSC
  • PDOT poly (3,4-ethylenedioxythiophene)
  • P3HT poly-3-hexylthiophene
  • synthons in particular carbazole or fluorene-based synthons that can be chemically modified in an easy manner, it is possible to prepare a wide range of amorphous molecules, carrier of holes, having good mobility. , energy levels suitable for regeneration of the photooxidized dye, and having optical and semiconductor properties suitable for use in DSSCs.
  • the interest of these synthons is the possibility of developing many ⁇ -conjugated organic materials, in particular thanks to the reactivity of the 9-position on the carbazole or fluorene ring.
  • the synthesis of these ⁇ -conjugated materials if they present complex structures can be carried out in a single step from said synthons and a well-chosen connector center.
  • the invention aims to provide a process for preparing ⁇ -conjugated materials from new synthons.
  • the invention also aims to provide new synthons and their manufacturing process.
  • the present invention relates to a process for synthesizing ⁇ -conjugated materials comprising a step of implementing a synthon of formula (I)
  • W represents either a group -CH R 5 -, or a group -N (H) -,
  • R 1 and R 2 are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group comprising
  • said groups may be substituted by at least one alkyl group-Ci 2 straight or branched, in particular methyl, or by alkoxy, Ci-Ci 2 straight or branched, in particular methoxy,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 3 and R 4 which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and which may comprise one or more heteroatoms chosen from O and S,
  • alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 5 is chosen from:
  • alkyl groups at. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • R 1 and R 2 which are identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group including
  • said groups may be substituted by at least one alkyl group-Ci 2 straight or branched, in particular methyl, or by alkoxy, Ci-Ci 2 straight or branched, in particular methoxy,
  • Ar i where Ari and Ar 2 , which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 1 and R 2 are in position 3 and / or 6 or 2 and / or 7 of the carbazole ring, then R 3 and R 4 are in position 1 and 5 or 4 and 8 of said ring.
  • the mono or polycyclic aromatic groups comprise from 6 to 50 carbon atoms. In a way advantageousously, they comprise from 6 to 18 carbon atoms and are mono-, bi- or tricyclic.
  • the carbocyclic group comprises more than one ring nucleus, the cyclic rings can be fused two by two or attached in pairs by ⁇ bonds. Two fused rings may be ortho-condensed or pericondensed.
  • the carbocyclic radical may comprise a saturated part and / or an aromatic part and / or an unsaturated part.
  • the (C 6 -C 8) aryl including phenyl, benzyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, tetrahydronaphthyl, fluorene and carbazole.
  • These mono- or polycyclic radicals, and especially mono-, bi- or tricyclic radicals may comprise one or more heteroatoms chosen from O, S and / or N, preferably 1 to 4 heteroatoms.
  • the monocycles or the monocycle constituting the heterocycle has from 5 to 12 ring members, more preferably from 5 to 10 ring members, for example from 5 to 6 ring members.
  • C 1 -C 12 or straight or branched (C 1 -C 2 ) alkyl said alkyl group may be saturated or unsaturated and may comprise one or more heteroatoms chosen from O and S , a saturated or unsaturated linear or branched chain of 1 to 15 carbons said carbon atoms may be replaced by one or more heteroatoms selected from O and S.
  • Examples may be mentioned by way of example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, neohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 1-methyl-1-ethylpropyl, heptyl, 1-methylhexyl, 1-propylbutyl, 4,4-dimethylpentyl, octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, 1-methylnonyl, 3,7-dimethyloct
  • alkoxy groups C 1 -C 12 alkyl or (Ci-Ci 2) alkoxy straight or branched represent an alkoxy group comprising 1 to 12 carbon atoms, said alkoxy groups may be saturated or unsaturated and may comprise one or more heteroatoms selected from O and S.
  • the term oligoether group is understood to mean oligomers whose organic repeating units are held together by ether functions (C-O-C).
  • the oligoethers according to the invention comprise two to five ether groups and from 2 to 4 repeating units.
  • oligoethers there may be mentioned diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol.
  • oligothioether group means oligomers whose organic repeating units are held together by thioether (C-S-C) functions.
  • the oliothioethers according to the invention comprise two to three thioether groups and from 2 to 4 repeating units.
  • oligothioethers mention may be made of ethanedithiol.
  • halogen is understood to mean an atom chosen from the group comprising bromine, chlorine, fluorine and iodine.
  • nitro group a group -NO 2 and sulfonate group, a group -S0 2 .
  • amine groups means primary (-NH 2 ), secondary or tertiary amines.
  • R 2 may be mentioned:
  • a compound of formula (I) in which R 1 and R 2 are each independently of one another is chosen from:
  • phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl and carbazolyl groups said groups possibly being substituted with at least one straight or branched C 1 -C 12 alkyl group, especially a methyl group,
  • Ra and Rb identical or different, each represent independently of each other:
  • b. is a straight or branched C 1 -C 12 alkyl group, said alkyl group possibly being saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy group may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S, in particular methoxy,
  • R 2 are each independently of one another, a group selected from the groups:
  • Ra and Rb identical or different, each represent independently of each other:
  • alkoxy group at. is a straight or branched C 1 -C 12 alkoxy group, said alkoxy group may be saturated or unsaturated and may comprise one or more heteroatoms chosen from O and S, in particular a methoxy group,
  • R 1 and R 2 are as previously defined.
  • R 1 and R 2 are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group comprising
  • aryl groups ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C 1 -C 5 alkyl group, in particular a methyl group,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • Ci-Ci 2 alkyl groups said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S, vs. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S,
  • R 3 and R 4 which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 6 represents either an alkyl group Ci-2 straight or branched, or an aryl group of C 6 -C 8, in particular a benzene group or methoxybenzene (anisole), or an amine protecting group, in particular a group benzyl, optionally substituted by an alkoxy group C1-C5 or an aryl group of C 6 -C 8 alkyl by a halogen, in particular fluorine or substituted by a straight or branched fluorinated C 1 -C 12 alkyl group, in particular trifluoromethyl (CF 3), or a bicyclic or tri-tetracyclic group comprising from 10 to 18 carbon atoms such as, for example, naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl.
  • the compounds prepared according to the process of the invention correspond to formula (Ib ')
  • R 1 and R 2 are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group comprising
  • aryl groups ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C 1 -C 5 alkyl group, especially a methyl group,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 3 and R 4 which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 6 represents either an alkyl group Ci-2 straight or branched, or an aryl group of C 6 -C 8, in particular a benzene group or methoxybenzene (anisole), or an amine protecting group, in particular a group benzyl, optionally substituted alkoxy C 1 -C 5 or an aryl group of C 6 -C 8 alkyl substituted by halogen, in particular fluorine or substituted by an alkyl group Ci-Ci 2 straight or branched fluorinated, in especially trifluoromethyl (CF3), or bistral, tri or tetracyclic group comprising from 10 to 18 carbon atoms, such as for example a naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl group.
  • the process of the invention also makes it possible to prepare ⁇ -conjugated materials corresponding to formula (Ia) or (Ib)
  • polyfunctional central unit means a unit carrying functions for grafting in position 9 of the carbazole ring or the fluorene ring.
  • functions that allow grafting mention may be made of iodine, bromine, chlorine atoms, tosylates, mesylates, etc.
  • polyfunctional central units it may be noted - C 6 H 4 -, biphenylene, terphenyl, fluorenyl, carbazolyl, oligooxyethylene derivative, these polyfunctional central units may or may not be substituted by one or more linear or branched C1-C12 alkyls.
  • n is an integer equal to or greater than 2, advantageously between 2 and 6, R 1 and R 2 , identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group comprising
  • aryl groups ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C 1 -C 5 alkyl group, in particular a methyl group,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 1 and R 2 are not simultaneously a hydrogen atom, R 3 and R 4 identical or different occupy the positions left free by Ri and R 2 and are chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 5 represents:
  • a) is a straight or branched C 1 -C 12 alkyl group, said alkyl groups may be saturated or unsaturated and may comprise one or more heteroatoms selected from O and S,
  • the interest of the various synthons used in the process according to the invention is the possibility of elaboration of many ⁇ -conjugated organic materials, in particular thanks to the reactivity of the 9-position of the carbazole ring and the 9-position of fluorene.
  • the ⁇ -conjugated organic materials derived from said synthons may be polyfunctional, ie they have a center connected to several synthons.
  • the process according to the invention gives a wide possibility of synthesis of new ⁇ -conjugated organic materials.
  • the synthesis of these ⁇ -conjugated materials is made easy by the use of the synthon since one can have access to certain ⁇ -conjugated materials of complex structures in a single step from this synthon.
  • ⁇ -conjugated materials have applications in optoelectronics, especially for charge transport and / or photon absorption. Examples that may be mentioned include OLEDs, organic transistors, organic photovoltaic cells, hybrid cells and perovskites cells.
  • R 1 and R 2 are respectively in position 3 and 6 or in position 2 and 7 of the ring and are chosen independently of each other in the group comprising
  • aryl groups said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, in particular a methyl group,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • Ci-Ci 2 alkyl groups straight or branched Ci-Ci 2 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 3 and R 4 which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from:
  • alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 5 is chosen from:
  • alkyl groups at. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • R 6 is alkyl C 1 -C 12 straight or branched, or an aryl group of C 6 -C 8, in particular a benzene group or methoxybenzene (anisole), or an amine protecting group, in particular a group benzyl, optionally substituted alkoxy C 1 -C 5 or an aryl group of C 6 -C 8 alkyl substituted by halogen, in particular fluorine or substituted with alkyl C 1 -C 12 straight or branched fluorinated, in particular, trifluoromethyl (CF 3), or bistral, tri or tetracyclic group comprising from 10 to 18 carbon atoms, for example a naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl group are new and form part of the invention.
  • CF 3 trifluoromethyl
  • the compounds of formula (I) may be prepared by any technique known to those skilled in the art from compounds available commercially or which may be prepared according to techniques known to those skilled in the art or described in the literature.
  • the first step (ii) is the iodination of positions 3 and 6 of carbazole in acetic acid at 85 ° C in the presence of potassium iodide and potassium iodate as described by Tucker, SHJ Chem. Soc. 1926, 129, 546. It is followed by a second step (i) which consists in protecting the amine at position 9 of the diiodocarbazole with a benzyl group in the presence of sodium hydride in anhydrous tetrahydrofuran (THF) at room temperature (Estrada, LA; Neckers, DC Organic Letters 2011, 13, 3304).
  • THF anhydrous tetrahydrofuran
  • a CN coupling makes it possible to fix the bis (4-methoxyphenyl) amine group at the 3 and 6 positions of the carbazole unit; this step is carried out in toluene at 110 ° C. in the presence of a palladium catalyst, tris-terbutylphosphine and sodium butyloxate (Yamamoto, T., Nishiyama, M., Koie, Y. Tetrahedron Letters 1998, 39, 2367).
  • the last step is a deprotection reaction to remove the benzyl group from the 9-position of the carbazole core to make the amine function available for later use; it is carried out in THF and dimethylsulfoxide (DMSO) in the presence of potassium and oxygen terbutylate (Haddach, AA, Kelleman, A. Deaton-Rewolinski, MV Tetrahedron letters 2002, 43, 399).
  • DMSO dimethylsulfoxide
  • the compounds of formula (I) as defined above can also be prepared by a process comprising:
  • R 3 and R 4 which are identical or different, are chosen from
  • R 3 and R 4 are as defined in claim 1 and
  • X, at position 2 and 7 of the fluorene or 3 and 6 carbazole represents a halogen atom, especially an iodine or bromine atom,
  • the amine protecting group GP is chosen from: a benzyl group, optionally substituted by a C1-C5 alkoxy group, acetyl groups, tert-butyloxycarbonyl (Boc) and carbamate.
  • R 6 represents a polycyclic group, in particular a bicyclic tri- or tetracyclic group comprising from 10 to 18 carbon atoms, for example a naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl group, are prepared from the corresponding compounds of formula (Ib) according to techniques known to those skilled in the art.
  • the subject of the invention is also ⁇ -conjugated materials of formula (Ibl)
  • aryl groups said aryl groups possibly being substituted with at least one straight or branched C 1 -C 5 alkyl group, in particular a methyl group,
  • Ari and Ar 2 which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from:
  • the hydrogen atom b. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • R 3 and R 4 which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from:
  • Ci-Ci 2 alkyl groups said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S,
  • alkoxy-Ci 2 straight or branched said alkoxy groups may be saturated or unsaturated and may contain one or more heteroatoms selected from O and S,
  • Q represents a spacer selected from the group consisting of: at. C1-C12 alkylenyl groups,
  • arylènyles groups is meant a arylènyle C 6 -C 8, unsubstituted or substituted with one or more C 1 -C 12.
  • the arylenyl group represents a fluorenyl group substituted with one or more C 1 -C 12 alkyls at the 9-position of fluorenyl.
  • the compounds of formula (Ibl) may be prepared by any technique known to those skilled in the art from the synthons of the invention, using products which are commercially available or which may be prepared according to techniques known to man of the art or described in the literature.
  • a very promising application of the present invention is the field of organic photovoltaics and particularly photovoltaic cells with dye or dye sensitized solar cell (DSSC).
  • the process according to the invention has already allowed the synthesis of a number of ⁇ -conjugated organic molecules, semiconductors whose use instead of the liquid electrolyte in the DSSC has given preliminary results very promising.
  • the best materials used under the same conditions as the market's reference molecule (spiro-OMeTAD) give comparable photovoltaic performances.
  • the synthon may also be used to develop dyes having similarities of chemical structures with the semiconductors derived from this same synthon. Having strong affinities between the semiconductor and the dye will increase the dye / semiconductor interactions, which is favorable for the pore filling of the sensitized Ti0 2 .
  • FIGS. 1 and 2 illustrate the invention.
  • FIG 1 shows dark-current-voltage (J-V) curves of devices using semiconductors comprising compounds 4-7 synthesized according to Examples 2-5 in combination with D102 dye according to Example 11.
  • FIG. 2 Current-voltage (VV) curves under illumination of devices using semiconductors comprising compounds 4 to 7 synthesized according to Examples 2 to 5 in combination with dye D102 according to Example 11.
  • Example 1 Synthesis of VV 3 , VV 3 , VV 6 , VV 6 , tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine (brick 3.6)
  • the first step is a protection of the 9-position amine of carbazole with a benzyl group according to Estrada, L.A. Neckers, D. C. Organic Letters 2011, 13, 3304.
  • the second step consists of the iodization of the 3 and 6 positions of the carbazole core according to Tucker, S.H. J. Chem. Soc. 1926, 129, 546.
  • a C-N coupling makes it possible to bind the bis (4-methoxyphenyl) amine group to the 3 and 6 positions of the carbazole unit according to Yamamoto, T.; Nishiyama, M. ; Koie, Y. Tetrahedron Letters 1998, 39, 2367.
  • the last step is a deprotection reaction to remove the benzyl moiety from the 9-position of the carbazole core to make the amino function available for later use according to Haddach, A.A. Kelleman, A.; Deaton-Rewolinski, M. V. Tetrahedron letters 2002, 43, 399.
  • the product is obtained in the form of a low-density white solid.
  • TLCs are made to check if the reaction is complete.
  • a solution of sodium thiosulfate at 5% is then added to the reaction mixture after returning to ambient temperature and the precipitate is recovered by filtration and then washed several times with water. The solid obtained is dried.
  • the product is obtained in the form of a white solid.
  • diphenylamine (10 mmol, 2.3 g, 1 eq)
  • diiodinated carbazole obtained in step 1.2.
  • tristbutylphosphine (0.2 mmol, 0.1 mL, 0.2 eq)
  • palladium acetate Pd (OAc) 2 ; 0.2 mmol, 5 mg, 0.2 eq)
  • the product is obtained in the form of a yellow powder
  • the benzylcarbazole derivative obtained at step 1.3. (2 mmol, 1.45 g, 1 eq) is added to a flask and the medium is then placed under an argon atmosphere. Dimethylsulfoxide (DMSO) is then added and the reaction mixture is stirred at room temperature. A solution of potassium tert-butoxide (KO'Bu) at 1M in THF (12 mmol, 1.4 g, 6 eq, ie 12 mL of a solution of KO'Bu at 1M in THF) is then added to the mixture. The argon inlet is stopped and oxygen is bubbled into the reaction medium which remains stirred at room temperature for about 3 hours. TLCs are made to see the progress of the reaction.
  • DMSO dimethylsulfoxide
  • the crude obtained is purified by precipitation in acetone to obtain a pale green solid.
  • Fluorene (4 g, 24 mmol, 1 eq) is dissolved in a mixture containing acetic acid (60 ml), water (13 ml) and sulfuric acid (2 ml) at 95 ° C. vs. After reducing the temperature to 80 ° C., the diiodine (4.2 g, 16.6 mmol, 0.7 eq) and the periodic acid (1.85, 8 mmol, 0.33 eq) are then added to the mixture. reaction which is then left stirring for about 1h. TLCs were performed to follow the evolution of the reaction. The precipitate formed was recovered by filtration and then washed with a saturated solution of NaHCO 3 and water. The crude solid obtained was recrystallized from n-hexane.
  • the product is obtained in the form of a white solid.
  • the diiodinated fluorene obtained in the preceding step (4.2 g, 10 mmol, leq), n-bromo-hexane (3.63 g, 22 mmol, 2.2 eq) and potassium tertbutoxide ( 3.36 g, 30 mmol, 3 eq) are dissolved in anhydrous THF (30 mL).
  • anhydrous THF (30 mL).
  • the reaction mixture is brought to 40 ° C and then left stirring overnight. TLCs were performed to follow the evolution of the reaction.
  • the reaction mixture is allowed to come to room temperature then poured into cold water.
  • the resulting crude was extracted with diethyl ether, the combined organic phases were washed with brine and dried with MgSO 4 . After evaporation of the solvent, the crude was purified by chromatographic column with eluent petroleum ether / ethyl acetate (9.5: 0.5).
  • the product is obtained in the form of a white solid.
  • the product is obtained in the form of a light yellow powder.
  • the product is obtained in the form of a white solid
  • the product is obtained in the form of a white solid.
  • the product is obtained in the form of a green powder
  • Compounds B and C are obtained according to the same protocol using respectively 1-bromopyrene or 1-fluoro-4-iodobenzene.
  • Example 8 Synthesis of 9,9 '- (propyl) bis (3 IM, IM 3, an IM, IM e, tetrakis (4-methoxyphenyl) -9H-carbazol-3,6-diamine) (compound 9)
  • Compound 10 was obtained according to the same protocol as that used in Example 8 using respectively 1,6 dibromohexane.
  • the yield obtained for the compound is 60%.
  • Compound 11 was obtained according to the same protocol as that used in Example 8 using respectively 1,12 dibromododecane.
  • the yield obtained for the compound is 84%.
  • Example 11 Efficiency of molecular glasses of Examples 2 to 5 as organic semiconductors in ssDSSC devices.
  • the four molecular glasses are The four molecular glasses:
  • ssDSSC solid DSSC photovoltaic devices
  • Puckyte et al Carboazole-based molecular glasses for efficient solid-state dye-sensitized
  • Device performance measurements are made in the dark and under illumination (AM 1.5 G).
  • the composition of the cell is as follows: FTO / TiO 2 / D102 / HTM / Ag.
  • Semiconductors are represented by hole transporting materials (HTM).
  • the solutions used for the development of the hole transport layer have a concentration of HTM of 200 mg / mL in chlorobenzene, in the presence of additives commonly used for DSSC namely lithium bis (trifluoromethane) sulfonimide (LiTFSI ) and 4-tert-butylpyridine.
  • additives commonly used for DSSC namely lithium bis (trifluoromethane) sulfonimide (LiTFSI ) and 4-tert-butylpyridine.
  • Jsc surface density of current (m A. cm '2 )
  • the characterizations were performed in the dark and under illumination (AM 1.5 G).
  • the four devices show a diode characteristic in the dark and a photovoltaic effect under illumination by the appearance of a photogenerated current (see Figures 1 and 2).
  • the short-circuit current densities obtained are between 4.17 mA.cm -2 and 7.45 mA.cm -2 and the values of the open circuit voltages are between 0.73V and 0.82V.
  • Photovoltaic conversion efficiencies range from 1.34% to 2.36%.
  • Compound 5 is the one which made it possible to obtain the best conversion yield which is 2.36%.

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