Patent Description:
The search for new donor: acceptor pairs for organic photovoltaic (OPV) applications is highly important for socio-economic and environmental reasons.

From the point of view of performance and stability, the composite couple of poly(<NUM>-hexylthiophene):[<NUM>,<NUM>]-phenyl-C<NUM>-methyl butyrate (P3HT:PCBM) has long been the standard bearer.

However the poor electronic correlation between the donor (P3HT) and the acceptor (PCBM), combined with numerous morphological instabilities at the heart of the heterojunction are two of the major problems that are tackled through diverse solutions proposed in the literature.

The search for a better correlation in the electronic properties ranges from minor modifications in the chemical structures of one of the pair components to complete replacement of the donor or acceptor molecule.

Due to the inherent difficulties of synthesising or grafting groups onto fullerene, the precursor of PCBM, numerous authors have sought to replace it.

Accordingly, graphene-based materials have rapidly appeared as good acceptor candidates, primarily because of their remarkable semiconducting properties.

In particular, <NPL>, disclose a series of hexabenzocoronene (HBC) derivatives containing Br, F, CF3 and aryl substituents said to be appropriate acceptors to be substituted to PCBM in the composite couple of P3HT : PCBM.

However, the short current circuit Jsc of this composite couple is quasi-null so that the efficacy of the OPV devices using this composite couple is also quasi-null. The efficacy depends from the product (Voc x Jsc x FF ) divided by the power in, where FF is the fill factor and the Voc is the open circuit Voltage. The FF is the product of the maxima of the voltage and current divided by the product of the Voc and the Jsc. Furthermore the donor and acceptor are a blend and are not covalently connected, therefore the charge transfer is hindered by this disorganition. Also, <NPL>, describe columnar systems in which the donor is an HBC modified by alkyl chains and the acceptor is a alkyl modified perylene and in which all other substituents are H, such an HBC. However, the electronic levels of the HBC moieties have not been modified through careful change of substituent groups to optimize the electronic efficacy nor have the donor and acceptor been covalently linked to provide structural stability and self-organization to optimize charge-collation and transfer to electrodes.

But, materials in organic photovoltaic cells should ideally be adapted and optimized for maximum efficiency at each stage of the process of converting solar energy into electricity.

In this context, the invention aims to propose materials for organic photovoltaic applications based on graphene enabling to obtain such a maximum efficiency.

For attaining this aim, the invention proposes a hexabenzocoronene-based compound of following formula I:
<CHM>.

Preferably in the hexabenzocoronene-based compound of the invention, R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical.

Still preferably in the hexabenzocoronene-based compound of the invention, R<NUM> and R<NUM> are identical and are a poly(<NUM>-oxypentylthiophene) substituent.

Again preferably in the hexabenzocoronene-based compound of the invention, R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are carboxylic groups.

The invention also proposes a donor: acceptor layer comprising a stack of hexabenzocoronene-based compound according to the invention.

A device comprising at least one hexabenzocoronene-based compound according to the invention is also proposed by the invention.

Preferably, this device is a photovoltaic cell.

The invention will be better understood and other advantages and characteristics thereof will appear more clearly when reading the following description which is made in reference to the figures in which:.

Based on a comparison between the band-structure of P3HT:PCBM and that of an ideal donor: acceptor pair, schematically represented in <FIG>, the key parameters to be optimized for obtaining a material adapted and optimized for maximum efficiency of an organic photovoltaic cell at each stage of the process for converting solar energy into electricity are briefly summarized as being:.

The inventors have now discovered that new graphene-based materials, namely hexabenzocoronene (HBCs), meet the requirements of the whole set of parameters that govern the efficiency of the organic photovoltaic (OPV) device from both electronic and oxidative stability points of view.

More precisely, hexabenzocoronene-based compound (HBC) having the formula I below:
<CHM>.

They are superior to PCBM by way of their two-dimensionality, they avoid micro aggregations resulting in a disruption of the morphology and a rupture of the active layer and the device, they increase exciton pathway lengths and facilitate charge transport.

This is due to the columnar structure of these compounds which provides a channel for the electron flux and thus enables charges to diffuse to the electrode through a favourable graphene/electrode interaction.

The columnar structure is obtained by the choice of the position and nature of the substituents R<NUM>, R<NUM>, R<NUM> and R<NUM> in formula I. Such a choice permits to obtain an optimal close stacking of the different layers of the HBC of the invention.

This columnar structure is very stable due to the choice of the substituents R<NUM>, R<NUM>, R<NUM> and R<NUM>.

Furthermore, all these substituents permit to fit the electronic levels of graphene of the HBC core so that these levels are in optimal phase for the electronic transfer from the donor system to the acceptor system.

Among the substituents which are chosen among a carboxylic group, a cyano group, an isocyano group, a cyanate group and a -F atom, for R<NUM>, R<NUM>, R<NUM> and R<NUM> a carboxylic group is particularly preferred because it is easier to graft on the HBC core.

In the compound of the invention, the positions <NUM> and <NUM> are occupied with a conductor polymer which is, in the invention, chosen among a poly(<NUM>-oxypentylthiophene) (P3OPT) and a poly(<NUM>-hexylthiophene) (P3HT) substituent. Thus R<NUM> and R<NUM> in formula I may be both a P3OPT or a P3HT or one of R<NUM> and R<NUM> is P3OPT and the other is P3HT.

However, preferably R<NUM> and R<NUM> are identical.

In the preferred compound of the invention of formula I, R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are a carboxylic group and R<NUM> and R<NUM> are also identical and are P3OPT substituents because when different layers of these compounde are formed, they are perfectly stacked.

The compound of the invention has the structure shown in <FIG>.

When stacked, the different layers formed of the compound of formula I are stacked as shown in <FIG> at the beginning of the stacking and as shown in <FIG> at the end of this stacking.

As one can see from <FIG>, the compound of the invention forms a compact stack while providing a columnar structure as shown on the right on of <FIG>.

Thus, by appropriate chemical functionalization of circular hexabenzocoronenes (circ-HBCs) the inventors have found an acceptor compound with electronic properties that match the donor compound, in the present case P3OPT or P3HT or a mixture thereof.

The substituents used for this chemical functionalization, which are to be grafted on positions <NUM>, <NUM>, <NUM> and <NUM> of the HBC core, are independently from each other chosen among a carboxylic (-COOH), cyano (-C ≡ N), isocyano (-N+ ≡ C-), cyanate (-O-C ≡ N) and -F atom.

Preferably, the substituent R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and more preferably, they are a carboxylic group.

The substituents R<NUM>, R<NUM>, R<NUM> and R<NUM> modulate the electronic position of the LUMO's acceptor according to the electronic HOMO-LUMO electronic position of the selected donor.

Moreover, their steric effect enables to obtain a columnar structure which channel the electron flux and thus enable charges to diffuse to the electrode.

The HOMO and LUMO energy of the two donor systems (P3HT and P3OPT) with an acceptor according to the invention which is an HBC of formula I in which R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are either an hexyl, CO<NUM>H, -CO<NUM>C<NUM>H<NUM> and -CO<NUM>C<NUM>H<NUM> are given in following table <NUM>.

Also, for comparison, the HOMO and LUMO energy of the same donor systems with an acceptor which is also an HBC but not according to the invention are given in following table <NUM>. These HBC based-compounds are triangular HBCs.

These HOMO and LUMO energy are also given in <FIG>.

In <FIG>, the donor systems P3HT and PCBM are compared to the ideal donor and in <FIG>, the donor system comprising a circ-HBC in which the substituents R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are carboxylic groups, are compared to that of the donor system P3HT-OR in which R is also a carboxylic group.

In this donor system, P3OPT is used as it has already showed a reduced intrinsic bandgap of <NUM> eV, making it possible to attain the theoretically optimised value of <NUM> eV, and is expected to demonstrate high stability and photostability.

In addition, P3OPT gives rise to a greater electronic delocalisation which can favour the transfer of charges between the donor and the acceptor.

The chosen acceptor, i.e. the two-dimensional HBC, also shows a greater electronic delocalisation than that of PCBM due to the greater accessibility of the involved π-orbitals. As a consequence, the global delocalisation of electrons over the whole donor:acceptor system favours the transfer of charges.

The electronic levels of grafted circ-HBC molecules which are compounds of the invention, are in good agreement with both an 'ideal electronic situation' (<FIG>), the experimental attempt and the data reported by <NPL>. Interestingly, the theoretical data gathered on HBC systems demonstrate that the shape and functionalization of these molecules lead to a wealth of possibilities to modulate the electronic properties on a wide energy range. Both triangular and circular functionalized HBCs could get close to the ideal configuration (regarding Voc and ΔELUMO) to match the target donor material P3OPT. However, it is clear that circ-HBC, allows much greater modularity when grafted by electron-withdrawing substituents. The systems constituted of a circ-HBC grafted with a CO<NUM>H substituent combined with P3OPT as donor material was calculated to possess a ΔELUMO of <NUM> eV and an open-circuit voltage of <NUM> eV. These two values, jointly to the Density Functional Theory (DFT) calculated HOMO/LUMO orbitals of the single P3OPT-circ-HBC(R=CO<NUM>H)- P3OPT of the invention depicted in <FIG> get very close to an ideal OPV system and provide an extremely good test candidate for future studies.

The intrinsic ability of the compound of the invention to form ordered stacks - the structure of which depends on the type of HBC substituents - is a useful property in that charge maybe more easily transponed to the electrodes.

Additional investigations on the π-stacking properties using ab initio, DFT and molecular dynamics (MD) simulations were carried out. While using graphene-based acceptor molecules for the ab initio and DFT simulations, molecular dynamic simulations were applied to the combined donor:acceptor molecule of the invention (P3OPT-circ-HBC(R=CO<NUM>H)-P3OPT, see <FIG> and <FIG>, to investigate the stability of these π-stacked arrangements of HBC molecules of the invention in solution with an organic solvent.

An evaluation of the geometrical and electronic properties was performed and compared with graphite itself. The inter-HBC equilibrium distances was calculated to be <NUM> and <NUM>Ǻ at ωB97XD/<NUM>-<NUM>* and SAPT-DFT [PBE0/cc-pVDZ] levels of calculation respectively. These results compare favourably to the inter-sheet distance of graphite (<NUM>Ǻ) and also to the results reported by <NPL> and references therein) using various levels of theory. Further performance enhancements for OPVs are expected to be possible from directly linking donor and acceptor in a single molecule due to improved electron transfer rates. To ensure already at an early stage that the changes to the HBC core does not in principle infringe the π-stacking, the behaviour of functionalized circ-HBC in solution was dynamically-simulated.

<FIG> shows the π-stacking of the functionalized circ-HBC of the invention at the start and <FIG> shows this π-stacking at the end of.

After equilibrating the system for <NUM> ns (releasing more and more parts of the systems), a convergence via energy and structural features is obtained.

For the production run of <NUM> ns, an average distance of <NUM>Ǻ between two circ-HBC molecules of the invention is obtained, which is in very good agreement with experimental (<NPL>) and theoretical (<NPL>, and <NPL>) results for similar systems. The π-stacked structure remains stable throughout the whole simulation time and the stacking of the molecules is illustrated in <FIG>, <FIG> provides the distribution function gz, in dependency of the z-coordinate.

The HBC based-compound of the invention was demonstrated to be a suitable model of graphene, its size and structure being well adapted to replace PCBM because of its two-dimensionality. In addition to its electronic properties, its columnar structure (which should resolve the weak efficiency observed by Gupta et al. with Graphene Quantum Dots) channels the electron flux and thus enable charges to diffuse to the electrode through a favorable graphene/electrode interaction. The influence of the substitution by side chains on the energy of the LUMO level of HBC provided exactly what the inventors were hoping to achieve: for a two component system consisting of a circ-HBC grafted with a -CO<NUM>H substituent as acceptor and P3OPT as donor, the obtained ΔELUMO = <NUM> and Voc = <NUM> eV, both excellent values to form a highly efficient solar cell.

Thus, the compound of formula I of the invention has been proved to be quite appropriate for forming the donor: acceptor layer.

<FIG> schematically shows such a donor: acceptor layer located between the two electrodes.

Accordingly, a donor: acceptor layer comprising at least one compound of formula I of the invention is also a subject matter of the invention as well as any device comprising at least one compound of formula I of the invention.

More particularly, this device is an organic photovoltaic cell.

A compound of formula I which is particularly preferred in the invention is the compound of the following formula I-<NUM>:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are a carboxylic group (-COOH), and R<NUM> and R<NUM> are identical and are chosen among a poly(<NUM>-oxypentylthiophene) (P3OPT) substituent and a poly(<NUM>-hexylthiophene) (P3HT) substituent.

The invention proposes three methods of synthesis of this compound of formula I-<NUM>.

The schema reaction of the first method of synthesis of the invention is as follows:
<CHM>.

This first method of synthesis according to the invention comprises the following steps:.

In this first method according to the invention, step e1) of introducing the carboxylic groups on the intermediate is carried out after the coupling of the polymer of formula (<NUM>) (P3HT) or of the polymer of formula (<NUM>) (P3OPT). And this grafting of the carboxylic groups is carried, in step e), by Friedel-Crafts acylation between an acid chloride and the compounds (<NUM>) or (<NUM>).

This Friedel-Crafts acylation could provoke attacks on the polymer chains grafted in step d), giving a lower yield.

In order to avoid such attacks on the polymer chain, a second process of the invention is a process wherein the introduction of the carboxylic groups is carried out before step e) of introduction of the polymer in the compound.

Thus, the invention proposes a second method of synthesis of the compound of formula I-<NUM> comprising the following steps:.

Preferably, in the first and second methods of the invention, step f) of cyclodehydrogenation of the compound of formula (<NUM>') or of the compound of formula (<NUM>') or of the compound of formula (<NUM>) of the compound of formula (<NUM>), is carried out by reacting these compounds with <NUM>,<NUM>-dichloro-<NUM>,<NUM>-dicyano-<NUM>,<NUM>-benzoquinone (DDQ).

But step f) may also be a step of reaction of the compound of formula (<NUM>') or the compound of formula (<NUM>') or of the compound of formula (<NUM>) or of the compound of formula (<NUM>) with FeCl<NUM>, dissolved in CH<NUM>NO<NUM>.

In the first and second methods of synthesis of the invention, step f) of cyclodehydrogenation is carried out on the intermediate in which all the substituents R<NUM>, R<NUM>, R<NUM> and R<NUM> are already grafted.

The presence of these substituents may render the final cyclodehydrogenation less effective, so that a lower yield is obtained.

It is why the invention also proposes a third method of synthesis of the compound of formula I-<NUM>.

In this third method, the step of cyclodehydrogenation is carried out before introduction of the carboxylic groups and of polymers (<NUM>) or (<NUM>), i.e. after step c) of formation of the bis-boronic ester intermediate.

Accordingly, the third method of synthesis of the compound of formula I-<NUM>, according to the invention, comprises the following steps:.

In all the methods of synthesis of the compound of formula I-<NUM>, according to the invention, preferably, in step c), the dioxaborolane derivative is <NUM>-isopropoxy-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-[<NUM>,<NUM>,<NUM>]dioxaborolane.

Also preferably, in all the method of synthesis of the compound of formula I-<NUM>, according to the invention, step b) is carried out in a microwave-heated apparatus at a temperature comprised between <NUM> and <NUM>, preferably at <NUM> and a power of between <NUM> and <NUM> W, preferably at <NUM> W during between <NUM> and <NUM> minutes and preferably during <NUM> minutes.

All the methods of synthesis of the compound of formula I-<NUM>, according to the invention, may furthermore comprise a step g) of synthesis of the polymer of formula (<NUM>) (P3HT) or of the polymer of formula (<NUM>) (P3OPT).

Otherwise stated, step g) may be a step of synthesis of the polymer of formula (<NUM>) (P3HT) which is carried out by Grignard Metathesis (GRIM) polymerization of <NUM>,<NUM>-dibromo-<NUM>-hexylthiophene or <NUM>,<NUM>-diiodo-<NUM>-hexylthiophene or <NUM>-bromo-<NUM>-iodo-<NUM>-hexylthiophene or <NUM>-iodo -<NUM>-bromo-<NUM>-hexylthiophene but most preferably <NUM>,<NUM>-dibromo-<NUM>-hexylthiophene.

But, step g) may also be a step of synthesis of polymer (<NUM>) (P3OPT) by the Grignard Metathesis (GRIM) polymerization of <NUM>,<NUM>-dibromo(<NUM>-oxypentylthiophene) or <NUM>,<NUM>-diiodo-(<NUM>-oxypentylthiophene) or <NUM>-bromo-<NUM>-iodo-(<NUM>-oxypentylthiophene) or <NUM>-iodo-<NUM>-bromo-(<NUM>-oxypentylthiophene) but most preferably <NUM>,<NUM>-dibromo-(<NUM>-oxypentylthiophene).

In order to give a better understanding of the method of the invention, examples of synthesis of the compound of formula I-<NUM> are given below.

This reaction is carried out according to the following reaction schema:
<CHM>.

The synthesis of polymer <NUM> is carried out by a Grignard Metathesis (GRIM) polymerization of <NUM>,<NUM>-dibromo(<NUM>-hexylthiophene) yielding to alpha-bromo-poly(<NUM>-hexylthiophene (P3HT) in which n may vary from is between <NUM> and <NUM> and preferably between <NUM> and <NUM> and ideally between <NUM> and <NUM>. This GRIM polymerization is carried out according to the method described by <NPL>.

Into a <NUM> flask equipped with a stirring bar is stirred for <NUM> at <NUM> a mixture of <NUM>,<NUM>-dibromo-<NUM>-hexylthiophene (<NUM>, <NUM>, <NUM> x <NUM>-<NUM> mol), freshly distilled THF (<NUM>) and isopropyl magnesium chloride (<NUM> in THF, <NUM>, <NUM> x <NUM>-<NUM> mol). The solution is diluted with THF (<NUM>) prior to the one-shot addition of <NUM>,<NUM>-bis(diphenylphosphino)propane nickel(II) chloride [Ni(dppp)Cl<NUM>] (<NUM> x <NUM>-<NUM> mol). The polymerisation is stirred for <NUM>, and terminated by the addition of <NUM> of HCl (<NUM>). The solution is dropped into methanol (<NUM>) and filtered into a Soxhlet thimble. The purple polymer is Soxhlet washed with methanol, then hexane, and Soxhlet recovered with THF. The polymer is then precipitated three times from THF in methanol and recovered over a glass frit.

This synthesis is carried out according to the following reaction schema:
<CHM>.

The synthesis of polymer (<NUM>) is a Grignard Metathesis (GRIM) polymerization of <NUM>-dibromo(<NUM>-oxypentylthiophene) yielding polymer <NUM> wherein n is comprised between <NUM> and <NUM>, inclusive, preferably between <NUM> and <NUM>, inclusive, and more preferably between <NUM> and <NUM>, inclusive.

This GRIM polymerization is carried out as disclosed in <NPL>.

Into a <NUM> flask equipped with a stirring bar is stirred for <NUM> at <NUM> a mixture of <NUM>,<NUM>-dibromo-<NUM>-oxypentylthiophene (<NUM> x <NUM>-<NUM> mol), freshly distilled THF (<NUM>) and isopropyl magnesium chloride (<NUM> in THF, <NUM>, <NUM> x <NUM>-<NUM> mol). The solution is diluted with THF (<NUM>) prior to the one-shot addition of <NUM>,<NUM>-bis(diphenylphosphino)propane nickel(II) chloride [Ni(dppp)Cl<NUM>] (<NUM> x <NUM>-<NUM> mol). The polymerisation is stirred for <NUM>, and terminated by the addition of <NUM> of HCl (<NUM>). The solution is dropped into methanol (<NUM>) and filtered into a Soxhlet thimble. The purple polymer is Soxhlet washed with methanol, then hexane, and Soxhlet recovered with THF. The polymer is then precipitated three times from THF in methanol and recovered over a glass frit.

The reaction schema used in this example is the following:
<CHM>.

This reaction is carried out according to method disclosed in <NPL>.

To a <NUM><NUM> round-bottom flask containing <NUM>,<NUM>-bis(<NUM>-bromophenyl)-<NUM>-propanone (<NUM>, <NUM>, <NUM> mmol) and benzil (<NUM> mmol) in dichloromethane (<NUM>) is added potassium hydroxide (<NUM>, <NUM> mmol) as a solution in methanol (<NUM>). The reaction is heated to reflux under nitrogen for <NUM> before being cooled in an ice bath. The mixture is introduced into <NUM> of ice cold methanol and the resulting solid <NUM>,<NUM>-bis(<NUM>-bromophenyl)-<NUM>,<NUM>-diphenylcyclopenta-<NUM>,<NUM>-dienone (<NUM>) is filtered to provide a dark purple solid (<NUM>, <NUM>% yield). <NUM>H NMR (<NUM>, CDCl<NUM>, ppm): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>). <NUM>C NMR (<NUM>, CDCl<NUM>, ppm): δ <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic-Br), <NUM> (s, aromatic=O).

In this step a), <NUM>,<NUM>-bis(<NUM>-chlorophenyl)-<NUM>-propane or <NUM>,<NUM>-bis(<NUM>-iodophenyl)-<NUM>-propane may also be used as starting compound (<NUM>) leading to the corresponding chlorinated or iodinated compound (<NUM>).

The reaction schema of this step is the following:
<CHM>.

This reaction is carried out according to the method disclosed in <NPL>.

To a microwave vial containing <NUM> (<NUM>, <NUM> mmol) in diphenyl ether (<NUM>) is added <NUM>,<NUM>-bisphenylacetylene (<NUM>, <NUM> mmol). This is microwave-heated (<NUM> and <NUM> W) for <NUM>. The vial is cooled with a positive pressure of air, and the resulting purple slurry is filtered and washed with <NUM> of diphenyl ether. Dichloromethane is used to dissolve and recover all the products present on the paper filter and the solvent is evaporated. Methanol is added to remove diphenyl ether and the solution is filtered to yield <NUM>,<NUM>-di(<NUM>-bromophenyl)-<NUM>,<NUM>,<NUM>,<NUM>-phenylbenzene (<NUM>) as white crystals (<NUM>, <NUM>% yield). <NUM>H NMR (<NUM>, CDCl<NUM>, ppm): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>). <NUM>C NMR (<NUM>, CDCl<NUM>, ppm): δ <NUM> (s, aromatic-Br), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic), <NUM> (s, aromatic). Compound (<NUM>) is also known as <NUM>-bromo-<NUM>'-(<NUM>-bromophenyl)-<NUM>',<NUM>',<NUM>'-triphenyl-<NUM>,<NUM>':<NUM>',<NUM>"-terphenyl.

To a solution of compound <NUM> (<NUM> mmol) in dry THF (<NUM>) under nitrogen at -<NUM>, n-BuLi (<NUM>/n-hexane, <NUM> mmol) is added and the resulting solution is stirred at -<NUM> for <NUM> minutes and then left to warm to <NUM> and held there for <NUM> minutes. Then the solution is cooled to -<NUM> and <NUM>-isopropoxy-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-[<NUM>,<NUM>,<NUM>]dioxaborolane (<NUM> mmol) is added and the reaction is stirred at -<NUM> for <NUM> minutes and then the cooling bath is removed so that the solution warms to room temperature while stirring for <NUM> minutes. The reaction is quenched with water (<NUM>) and the resulting mixture is extracted with dichloromethane. The combined organic layers are washed with brine, dried with MgSO<NUM> and concentrated under reduced pressure. The residue is purified by passing through a column (silica gel, aluminium oxide, dichloromethane) to give compound <NUM> as a white solid, yield = <NUM> %).

The reaction schema of this Suzuki-Miyaura coupling is the following:
<CHM>.

The method disclosed in this document has been changed by way of adding a polymer in place of small molecules.

A mixture of compound <NUM> or <NUM> (<NUM> mmol), compound <NUM> (<NUM> mmol), K<NUM>CO<NUM> (<NUM>/H<NUM>O, <NUM>, <NUM> mmol) and Aliquat® <NUM> (<NUM>, <NUM> mmol) in toluene (<NUM>) is degassed three times via 'freeze-pump-thaw' cycles. Pd(PPh<NUM>)<NUM> (<NUM> mmol) is added quickly and the reaction mixture degassed three times again via 'freeze-pump-thaw' cycles. The reaction is refluxed under argon for <NUM> days. Then, a degassed solution of <NUM> or <NUM> (<NUM> mmol) in toluene (<NUM>) is added into the reaction mixture via a syringe.

The reaction mixture is poured into a mixture of methanol (<NUM>) and concentrated aqueous HCl solution (<NUM>) and stirred overnight. The resulting black solid is filtered off and subjected to Soxhlet extraction for <NUM> days in acetone. The residue is redissolved in hot THF and precipitated again in methanol. The solid is filtered, washed with.

Into a nitrogen flushed vessel containing <NUM> or <NUM> (<NUM> mmol) in dichloromethane (<NUM>) is added CH<NUM>OCOCl (<NUM> mmol) followed by a solution of FeCl<NUM> (<NUM> mmol) in dichloromethane (<NUM>). The solution is stirred under reflux for <NUM>. After that time the reaction is filtered, and the resulting solid is dissolved in dichloromethane (<NUM>) and precipitated in methanol (<NUM>), and reprecipitated in the same manner, and dried under reduced pressure to the final product.

This reaction is based on the method disclosed in <NPL>.

A solution of <NUM> or <NUM> in dichloromethane (<NUM>) containing protic acid (<NUM>% v/v) or Lewis acid (~<NUM> equiv. ) at ~<NUM> is treated with DDQ (<NUM> equivalent per C-C bond formation), and the solution immediately took on a dark- green coloration. The progress of the reaction is monitored by TLC and <NUM>H NMR spectroscopy. After completion of the reaction, it was quenched with a saturated aqueous solution of NaHCO<NUM> (<NUM>). The dichloromethane layer was separated and washed with water and brine solution and dried over anhydrous MgSO<NUM> and filtered. Removal of the solvent in vacuo afforded the crude product.

This method is used in order to avoid attacks on the polymer chains present in compound (<NUM>) or (<NUM>) obtained in examples <NUM> and <NUM> during step e).

As already stated, in order to avoid such attacks, the introduction of the carboxylic groups (step e) of the first method of synthesis according to the invention) is carried out before step d) of the first method of synthesis of introduction of the polymers in the intermediate compound.

Into a nitrogen flushed vessel containing <NUM> (<NUM> mmol) in dichloromethane (<NUM>) is added CH<NUM>OCOCl (<NUM> mmol) followed by a solution of FeCl<NUM> (<NUM> mmol) in dichloromethane (<NUM>). The solution is stirred under reflux for <NUM>. After that time the reaction is filtered, and the resulting solid is dissolved in dichloromethane (<NUM>) and precipitated in methanol (<NUM>), and reprecipitated in the same manner, and dried under reduced pressure to the final product.

Then, the step of introduction of the polymer in the intermediate compound thus obtained is carried out and the other steps are the same as in the first method of the invention.

In this example, the final step of cyclodehydrogenation of the first and second methods of synthesis of the invention is carried out before the introduction of the carboxylic groups.

Thus, step noted f) in the first and second method of the invention is carried out, in the third method of the invention, after step d) of the first method of the invention or after e1) of the second method of the invention, and step e) of the first method of the invention and step d1) of the second method of the invention is the final step.

This step of cyclodehydrogenation is noted e2) in the third method of the invention. This step is followed by the step of introduction of the carboxylic groups by Friedel-Crafts acylation noted f1) in the third method of the invention.

A <NUM> two necked round bottom flask is charged with <NUM> mmol of <NUM> or <NUM> with <NUM> of CH<NUM>Cl<NUM>. The solution is flushed with argon. FeCl<NUM> (<NUM> mmol) dissolved in CH<NUM>NO<NUM> (<NUM>) is added dropwise. After <NUM>, the mixture is quenched with a large excess of methanol and the precipitate is filtered. The resulting yellow solid is redissolved in dichloromethane and filtered through a short pad of silica gel and dried under vacuum.

Step a) to d) are the same as in the first method of the invention.

The Voc (Open circuit Voltage) and ΔELUMO of the compounds obtained in examples <NUM>-<NUM> have been determined.

These Voc and ΔELUMO values of compounds of examples <NUM>-<NUM> are reported in following table <NUM>, together with the Voc and ΔELUMO of compounds 10b and 10c of Jones et al. and of a non substituted HBC.

As can be seen from table <NUM>, the compounds 10c and 10b exhibit ΔELUMO which is very superior to <NUM> eV, so that they are not candidates for OPV devices and the ΔELUMO of the HBC in which R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM> and R<NUM> is to low. In contrast, the ΔELUMO of the compounds of the invention are close to <NUM> eV.

These results clearly demonstrate that the compounds of the invention which have a columnar structure are the best adapted for obtaining an ideal Voc, due to the particular choice of the R<NUM>, R<NUM>, R<NUM> and R<NUM> substituents and that this particular choice associated with the particular choice of the R<NUM> and R<NUM> substituents permits an ideal and simultaneous transfer of charges between the donor and the acceptor in an OPV device.

Claim 1:
A Hexabenzocoronene-based compound of following formula I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently from each other chosen among a carboxylic (-COOH) group, a cyano (-C ≡ N) group, an isocyano (-N+ ≡ C-) group, a cyanate (-O-C ≡ N) group and a -F atom, preferably R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical, and more preferably R<NUM>, R<NUM>, R<NUM> and R<NUM> are identical and are carboxylic groups;
R<NUM> and R<NUM> are, independently from each other, chosen among a poly(<NUM>-oxypentylthiophene) (P3OPT) substituent and a poly(<NUM>-hexylthiophene) (P3HT) substituent, preferably R<NUM> and R<NUM> are identical and more preferably R<NUM> and R<NUM> are identical and are both a poly(<NUM>-oxypentylthiophene) substituent.