HETEROHELICENES SHOWING PROPERTIES OF DELAYED FLUORESCENCE AND CIRCULARLY POLARIZED LIGHT

Abstract

The present invention relates to molecules having both the properties of thermally activated delayed fluorescence (TADF) and circularly polarized light (CPL) emission. The invention also relates to the use of such molecules as photocatalysts or as dopants, in particular in the emitting layers of light-emitting diodes (OLEDs), as well as electroluminescent devices or light-emitting diodes (OLEDs) comprising such compounds. Figure for abstract: None

Description

Title of the invention: HETEROHELICENES EXHIBITING DELAYED FLUORESCENCE AND CIRCULARLY POLARIZED LIGHT EMISSION PROPERTIES Technical field of the invention

[0001] The present invention relates to novel organic molecules having both the properties of thermally activated delayed fluorescence (TADF) and circularly polarized light emission (CPL).

[0002] The invention also relates to the use of such molecules as photocatalysts, fluorescent probes, in particular for biology, or dopants, in particular in the emitting layers of light-emitting diodes (OLEDs), as well as electroluminescent devices or light-emitting diodes (OLEDs) comprising such molecules. Technical background

[0003] The search for molecules with delayed fluorescence properties is at the heart of the development of efficient, low-energy-cost light-emitting devices. These molecules, used pure or as dopants for the emitting layers of light-emitting diodes (OLEDs or Organic Light-Emitting Diodes in English), make it possible to manufacture light devices with a theoretical internal efficiency of 100% (meaning that all the charges injected in the form of current are returned in the form of light) compared to only 25% for a conventional fluorophore.

[0004] Until now, the emitting molecules that made it possible to achieve such yields were phosphorescent molecules involving organometallic complexes using rare metals such as iridium or platinum.

[0005] There are now numerous publications and patents highlighting the potential of purely organic TADF molecules as dopants for OLEDS.

[0006] For reasons of both manufacturing cost and sustainability, thermally activated delayed fluorescence (TADF) molecules, which can be purely organic, therefore represent a target of choice for researchers in a field experiencing rapid economic expansion thanks to their applications for low-energy lighting and high-resolution display devices.

[0007] Furthermore, the development of organic molecules that can emit circularly polarized light (CPL) is also a field that has been expanding rapidly in recent years. In this context, it is complexes involving lanthanides that make it possible to obtain the best performances in terms of degree of light polarization. However, much research is currently being conducted to develop purely organic CPL-emitting molecules to limit manufacturing costs and facilitate their incorporation into devices. Indeed, these small chiral molecules have strong application potential since they can be used in the design of advanced technology devices allowing, for example, optical information storage, 3D display or document security.

[0008] Furthermore, in the field of application of OLEDs relating to display, molecules having both delayed fluorescence and circularly polarized light emission properties are particularly attractive. Indeed, in order to limit the loss of brightness due to the reflection of external light, optical systems are used in display devices. These optical systems are most often composed of a delay plate (quarter-wave plate) and a polarizer, the combination of the latter makes it possible to cancel the reflection on the OLED of the external light component. However, a significant part of the light intensity produced by the molecule in the emitting layer of the OLED is lost for a molecule not emitting circularly polarized light.

[0009] Circularly polarized light emitting molecules are not only characterized by their quantum yield <bF(proportion de lumière émise après excitation) mais également par le facteur de dissymétrie lgiuml rendant compte de l’amplitude de la polarisation circulaire. Cette valeur de gium est comprise entre -2 et 2, la valeur 0 représente une absence de polarisation circulaire. Pour un fluorophore purement organique, la valeur de lgiuml est typiquement comprise entre 10 4 et

[0010] 102. At the moment very few organic molecules have high values both of <bF (supérieur à 50% et idéalement proche de 100 %) et de lgiuml (idéalement supérieur ou égal à 103). Dans le contexte de la présente invention, le rendement quantique se définit comme suit :

[0011] [Chem.l] Number of photons emitted ----------------------— sj 00 Number of photons absorbed

[0012] It is known that delayed fluorescence emission (TADF) is possible if the energy difference between the lowest energy singlet and triplet excited states (AEst) of the fluorescent molecule is small (less than 500 meV). The value of AESTest is proportional to the overlap integral between the frontier orbitals (OF in the rest of the presentation) HOMO and LUMO (for respectively, Highest Occupied and Lowest Unoccupied Molecular Orbital in English) of the molecule. Thus, several molecular structures have been proposed in the literature to limit the overlap between these OFs. The most commonly used structure is based on the use of donor-acceptor (DA) type molecules where the dihedral angle between these two entities is as close as possible to 90°. This makes it possible to limit the overlap of the OFs, the HOMO being mainly located on the electron donor and the LUMO on the acceptor. Thus, the first examples of organic molecules with this structure were published by Adachi et al., (Adachi et al., Nature 2012, 492, 234). An example is presented in [Fig. 1]. Here it is the steric constraint existing between the carbazoyl units ( ) and the terephthalonitrile part ( N< „N ) which allows to impose an adequate dihedral angle between the patterns .....ï' donors and the acceptor.

[0013] Another method to limit the overlap of OFs is based on the so-called "multi-resonance" effect. It is produced by the presence of boron and nitrogen atoms in a polycyclic structure. Hatekeyama et al. (Hatekeyama et al., Adv. Mater. 2016, 28, 2777-2781) thus synthesized the molecule presented in [Fig.2] which exhibits TADF properties.

[0014] In 2015-2016, the first molecular structures allowing the combination of TADF and CPL properties appeared and the team of inventors is one of the pioneers in this field (G. Pieters et al., J. Am. Chem. Soc. 2016, 138, 12, 3990-3993). The inventors recently published a journal article describing all the molecular designs allowing the combination of these two properties (G. Pieters et al., Adv. Funct. Mater. 2021, 31, 2010281).

[0015] The need for new molecules that are both delayed fluorescence emitters and circularly polarized light emitters still remains.

[0016] There is therefore a real need for molecules, in particular, organic molecules - emitting thermally activated delayed fluorescence (TADF), and - emitting circularly polarized light (CPL) characterized by high values ​​of both quantum yield <t>F greater than or equal to 50% in the solid state, and ideally close to 100%, and emission asymmetry factor accounting for the amplitude of circular polarization lgiuml (greater than or equal to 103 in solution), and - exhibiting differential absorption properties of circularly polarized light (circular dichroism) as a function of wavelength characterized by the absorption asymmetry factor (gabs), and

[0017] - having good solubility in organic solvents. There is, moreover, a real need for organic molecules with the aforementioned properties, which are durable, simple to produce, easily achievable on an industrial scale, with a manufacturing cost lower than the cost for known molecules, in particular avoiding the use of noble metals (such as Pd). Summary of the invention

[0018] The present invention relates to a molecule of formula (I)

[0019] in which

[0020] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0021] with Rb R2, R3, R4, R5, R6, R7, Rs, R9, Rio, R11 and R[2, identical or different, representing a hydrogen atom, a deuterium, a halogen atom chosen from F, Cl, Br and I, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0022] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0023] with

[0024] Rn, Ru, Rb, Ri6, Rn, Ri8, R19, R3i, R32, R33 and R34, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0025] D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0026] T representing a heteroatom chosen from the group formed by O, S, and CRR0 with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0027] L representing a heteroatom chosen from the group formed by O and S;

[0028] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0029] with

[0030] R20, R2i, R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0031] D' representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0032] T' representing a heteroatom chosen from the group formed by O, S, and CR'R'o with R' and R'o, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, and

[0033] L' representing a heteroatom chosen from the group formed by O and S; \ yJ represents the point of attachment of the atoms to the rest of the molecule by a bond covalent.

[0034] (Hetero)helicenes have a very high optical rotation due to the axial chirality induced by their helical conformation. The chemical structure of the compound of formula (I) extends to all possible configurational isomers that can be obtained by varying the configuration of the individual chiral centers, axes or surfaces of the compound of formula (I).

[0035] Generally, (hetero)helicenes are obtained in racemic form (50:50 mixture of the two P / M mirror images) and are then separated by high pressure liquid chromatography (HPLC) on chiral stationary phase.

[0036] (Hetero)helicenes are molecules with axial chirality. This property is also called "helicity", since the axis of the molecule has a helical geometry. A right-handed helix is ​​denoted P (plus) or A, a left-handed helix is ​​denoted M (minus) or A. These P / M or A / A notations are used in particular for molecules that truly have a helix shape such as (hetero)helicenes (Shen, Y.; Chen, C.-F. Helicenes: Synthesis and Applications. Chem. Rev. 2012,112 (3), 1463-1535).

[0037] The new molecules of formula (I) have a strong potential for application as a dopant in the emitting layer of organic light-emitting diodes (OLEDs) but also potentially as photocatalysts or fluorescent probes for biology.

[0038] These are new helical molecular architectures (heterohelicales) with delayed fluorescence emission (TADF) and circularly polarized light (CPL) properties.

[0039] The invention also relates to the use of a compound of formula (I), as a photocatalyst or as a dopant, in particular in the emitting layers of light-emitting diodes (OLEDs).

[0040] It further relates to an electroluminescent device or a light-emitting diode (OLED) comprising a compound of formula (I). Brief description of the figures

[0041] Other characteristics and advantages of the invention will appear during the reading of the detailed description which follows for the understanding of which reference will be made to the appended drawings in which:

[0042] [Fig. 1] represents a TADF molecule published by Adachi et al. of the donor-acceptor (DA) type where the dihedral angle between these two entities is as close as possible to 90°. In this molecule, the steric constraint existing between the carbazoyl units (donor) and the terephthalonitrile part (acceptor) makes it possible to impose an adequate dihedral angle between the donor units and the acceptor.

[0043] [Fig.2] represents a CPL and TADF molecule described by Hatekeyama et al.

[0044] [Fig. 3] represents the spectrum of a) the mixture of diastereoisomers of the intermediate imines Intl of Example 1, and b) the mixture of diastereoisomers of the compounds after hydrolysis (ketone form).

[0045] [Fig.4] represents the synthesis of symmetrical molecules (heterohelicenes) of formula (I) (molecule 3).

[0046] [Fig.5] represents the synthesis of the non-symmetrical molecule (heterohelicene) of formula (I) (molecule 6).

[0047] [Fig.6] represents the fluorescent decline measured after degassing of the helicenes (S)- BN-(M / P)-Helicene 1 and BP-(P / M)-Helicene 5 in toluene (10 5M). Fluorescence and phosphorescence emission decay curves are obtained in a single step by combining the time-correlated single photon counting (TCSPC) method and multichannel scanning triggered accumulation techniques, respectively. The device consists of a titanium sapphire Ti:Sa oscillator (Spectra Physics, Mai Taï) emitting 100 fs pulses at 940 nm (80 MHz frequency). The repetition rate is reduced to 20 MHz by a pulse selector, and a nonlinear second harmonic generation (SHG) crystal generates the desired wavelength (GWU Lasertechnik, UHG-23-PSK). The emitted photons are collected at 90° through a magic angle polarizer and a monochromator. The incoming photons are processed with a microchannel plate photomultiplier (MCP-PMT R3809U-50, Hamamatsu) and a TCSPC module (SPC-630, Becker & Hickl).

[0048] Detailed description of the invention The present invention aims to meet the needs identified above by providing a molecule of formula (I)

[0049] in which

[0050] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by R3

[0051] with Rb R2, R3, R4, R5, R6, R7, Rs, R% Rio, R11 and R[2, identical or different, representing a hydrogen atom, a halogen atom chosen from F, Cl, Br and I, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0052] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0053] with

[0054] Rn, Ru, Rn, Ri6, Rn, Ri8, R19, R3i, R32, R33 and R34, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0055] D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0056] T representing a heteroatom chosen from the group formed by O, S, and CRR0 with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0057] L representing a heteroatom chosen from the group formed by O and S;

[0058] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0059] with

[0060] R20, R2i, R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0061] D' representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0062] T' representing a heteroatom chosen from the group formed by O, S, and CR'R'o with R' and R'o, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, and

[0063] L' representing a heteroatom chosen from the group formed by O and S; represents the point of attachment of atoms to the rest of the molecule by a bond covalent.

[0064] The molecules of formula (I) have interesting chiroptical properties: a circular dichroism with asymmetry factors in absorption, gabs, up to 1.2 x 102 and in emission, gium, up to 1.4 x 103.

[0065] The chemical structure of the molecule of formula (I) extends to all possible functional positional isomers that can be obtained by moving a functional group to different carbons in the carbon chain, and to all possible configurational isomers that can be obtained by varying the configuration of individual chiral centers, axes, or surfaces of the molecule of formula (I).

[0066] The present invention therefore extends to all isomers of the molecules of formula (I), in particular to all position, function and configuration isomers.

[0067] The molecules of formula (I) have the advantage of being both emitters via delayed fluorescence (TADF) and emitters of circularly polarized light (CPL) since they are made up of a helical unit, composed of a symmetrical or non-symmetrical [7]-heterohelicene attached to a unit of the 2,2'-biphenol, BINOL, spiro biphenol type, or a bicylic unit with fused rings.

[0068] For the purposes of the present invention, the term "alkyl" means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. Examples of saturated, linear or branched alkyl that may be mentioned are: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl radicals and their branched isomers.

[0069] For the purposes of the present invention, the term "cyclic alkyl" means a saturated, optionally substituted, cyclic carbon radical comprising 3 to 12 carbon atoms, for example 3 to 10 carbon atoms, for example 3 to 8 carbon atoms. Examples of cyclic alkyl that may be mentioned are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl and adamantyl radicals.

[0070] The term "aryl" denotes a mono- or polycyclic aromatic substituent comprising from 6 to 20 carbon atoms. The aryl group may comprise, for example, 6 to 10 carbon atoms. For example, phenyl, benzyl, naphthyl, binaphthyl, phenanthrenyl, pyrenyl, anthrancenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl and p-methoxyphenyl, o-methoxybenzyl, p-methoxybenzyl, m-methoxybenzyl, o-methylbenzyl, p-methylbenzyl and m-methylbenzyl may be mentioned.

[0071] The term “alkoxy” denotes an -O-alkyl group in which the alkyl radical is as defined above.

[0072] The alkyl and aryl radicals may be optionally substituted by one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy groups (-O-aryl); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more carbonyl groups (-CO-alkyl); one or more alkyl radicals; one or more aryl radicals; with alkyl, and aryl as defined in the context of the present invention.

[0073] It should be noted that in all the substituents, radicals, groups and groups, etc. cited and / or defined in the context of the present invention, one or more hydrogen atoms may optionally be replaced by one or more deuterium (¾).

[0074] The representation " " as used herein in relation to an atom, group, substituent or chemical moiety, is intended to represent the covalent bond by which said atom, group or chemical moiety is covalently bonded to another group or chemical moiety.

[0075] Thus, in the molecules of the invention, \ represents the point of attachment of the atoms to the rest of the molecule by a covalent bond.

[0076] According to a first embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0077] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by R, Ri

[0078] with

[0079] Rb R2, R3, R4, R5, Re, R7, Rs, R% Rio, R11 and R[2, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted.

[0080] In a variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, R8, R9, R10, Ru and R[2, identical or different, represent a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms.

[0081] In another variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R12, identical or different, represent

[0082] - a hydrogen atom,

[0083] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0084] - a phenyl.

[0085] According to a second embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0086] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by » r. with Ri, R2, R3, R4, R5, Rg, R7, R8, R9, Rio, Ru and Ri2, representing a hydrogen atom.

[0087] According to a third embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0088] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0089] with R2, R3, R4, R5, R6, R?, and R8, representing a hydrogen atom.

[0090] According to a fourth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0091] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0092] with

[0093] Rn, Ru, Rb, Rie, Rn, Ris, R19, R31, R32, R33 and R34, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms carbon, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0094] D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0095] L representing a heteroatom chosen from the group formed by O and S.

[0096] In a variant of this embodiment, Rn, RM, R[5, R[6, Rn, Ri8, Ri9, R3B R32 , R33 and R34, identical or different, represent a hydrogen atom, an alkyl radical containing 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group contains 1 to 6 carbon atoms, an aryl radical containing 6 to 10 carbon atoms.

[0097] In another variant of this embodiment, Rn, R[4, Ri5, Ri6, Rp, R[8, R[9, R3[, R32, R33 and R34, identical or different, represent

[0098] - a hydrogen atom,

[0099] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0100] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0101] - a phenyl.

[0102] According to a fifth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0103] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0104] with

[0105] Rn, Rm, Rb, Rb, Rn, Ri8, Ri9, representing a hydrogen atom, and

[0106] D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+.

[0107] According to a sixth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0108] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0109] with

[0110] Rn, Ris, Rie, Ris, R19, representing a hydrogen atom,

[0111] Ru,, Rn, represents a phenyl, and

[0112] D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+.

[0113] According to a seventh embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0114] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0115] with

[0116] Rn, Ru, Rb, Rb, Rn, Rb, Rb, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0117] D representing a carbonyl (C=O) an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and

[0118] T representing a heteroatom chosen from the group formed by O, S, and CRR0 with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted.

[0119] In a variant of this embodiment, Rn, Ru, Ris, Rie, Ru, Ri8, and R[9 , identical or different, represent a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms.

[0120] In another variant of this embodiment, Rn, RM, R[5, R[6, Rn, R[8, and Ri9, identical or different, represent

[0121] - a hydrogen atom,

[0122] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0123] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0124] -unphenyl.

[0125] According to an eighth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0126] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0127] Rn, Ru, Rb, Ri6, Rn, Ri8, and R19 represent a hydrogen atom,

[0128] D represents a carbonyl (C=O), an imine of formula C=NH or C=NCH3, a iminium of formula C=NH2+ or C=NHCH3+, and

[0129] T represents O.

[0130] According to a ninth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0131] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0132] with

[0133] R20, R2i, R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0134] D' representing a carbonyl (C=O), and

[0135] L' representing a heteroatom chosen from the group formed by O and S.

[0136] In a variant of this embodiment, R2o, R2i, R22, R23, R24, R2s, R26, R27, R28 , R29 and R30, identical or different, represent a hydrogen atom, an alkyl radical containing 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group contains 1 to 6 carbon atoms, an aryl radical containing 6 to 10 carbon atoms.

[0137] In another variant of this embodiment, R20, R2i, R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, represent

[0138] - a hydrogen atom,

[0139] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0140] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0141] - a phenyl.

[0142] According to a tenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0143] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0144] with

[0145] R2o, R2i, R22, R23, R24, R25, and R26, representing a hydrogen atom, and

[0146] D' representing a carbonyl (C=O).

[0147] According to an eleventh embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0148] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0149] with

[0150] R2q, R22, R23, R25, and R26, representing a hydrogen atom,

[0151] R2i, R24, represents a phenyl, and

[0152] D' representing a carbonyl (C=O).

[0153] According to a twelfth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0154] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0155] with

[0156] R2q, R2i, R22, R23, R24, R25, and R26, identical or different, representing an atom hydrogen, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, a aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0157] D' representing a carbonyl (C=O), and

[0158] T' representing a heteroatom chosen from the group formed by O, S, and CRR0 with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted.

[0159] In a variant of this embodiment, R20, R2i, R22, R23, R24, R25, and R26, identical or different, represent a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms.

[0160] In another variant of this embodiment, R20, R21, R22, R23, R24, R25, and R26, identical or different, represent

[0161] - a hydrogen atom,

[0162] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0163] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0164] - a phenyl.

[0165] According to a thirteenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0166] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0167] R20, R2i, R22, R23, R24, R25, and R26, represent a hydrogen atom,

[0168] D' represents a carbonyl (C=O), and

[0169] T' represents O.

[0170] According to a fourteenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0171] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0172] with RB R2, R3, R4, R5, R6, R7, R8, R% Rio, R11 and R12, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0173] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0174] with Rn, R[4, Ri5, Ri6, Rn, R[8, R[9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0175] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0176] with R20, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, a radical aryl containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0177] D and D' represent a carbonyl (C=O).

[0178] According to a fifteenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0179] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0180] with Rb R2, R3, R4, R5, R6, R7, R8, R% Rio, R11 and R[2, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0181] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0182] with Rn, R[4, R15, Ri6, Rn, R[8, R[9, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0183] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0184] with R2o, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms,

[0185] D and D' represent a carbonyl (C=O).

[0186] In a variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R[2, identical or different,

[0187] represent

[0188] - a hydrogen atom,

[0189] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0190] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0191] - a phenyl.

[0192] In another variant of this embodiment, Rn, RM, R[5, R[6, Rn, Ri8, Ri9, identical or different, represent

[0193] - a hydrogen atom,

[0194] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0195] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0196] -unphenyl.

[0197] In another variant of this embodiment, R20, R2i, R22, R23, R24, R25, and R26, identical or different, represent

[0198] - a hydrogen atom,

[0199] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0200] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers, [0201 ] - a phenyl.

[0202] According to a sixteenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0203] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0204] with Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R[2, representing a hydrogen atom;

[0205] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0206] with Rn, Ru, R[5, R[6, Rn, Ri8, Ri9, representing a hydrogen atom;

[0207] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0208] with R20, R2i, R22, R23, R24, R25, R26, representing hydrogen atom,

[0209] D and D' represent a carbonyl (C=O).

[0210] According to a seventeenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0211] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0212] with Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R[2, representing a hydrogen atom;

[0213] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0214] with Rn, R[5, R[6, Ri8, Ri9, representing a hydrogen atom, and Ru, Rn, representing a phenyl;

[0215] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0216] with R20, R22, R23, R25, and R26, representing a hydrogen atom,

[0217] R2i, R24, represents a phenyl, and

[0218] D and D' represent a carbonyl (C=O).

[0219] According to an eighteenth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0220] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0221] with Rb R2, R3, R4, R5, R6, R7, R8, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0222] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0223] with Rn, R[4, R15, Ri6, R[7, R[8, R[9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0224] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0225] with R2o, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0226] D and D' represent a carbonyl (C=O).

[0227] According to a nineteenth embodiment of the invention,

[0228] the molecule of formula (I) as defined above, is characterized in that

[0229] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0230] with Rb R2, R3, R4, R5, R6, R7, and R8, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0231] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0232] with Rn, Ru, R[5, R[6, Rn, Ri8, Ri9, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0233] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0234] with R2o, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms.,

[0235] D and D' represent a carbonyl (C=O).

[0236] In a variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, and R8, identical or different, represent

[0237] - a hydrogen atom,

[0238] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0239] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0240] - a phenyl.

[0241] In another variant of this embodiment, Rn, R[4, Ri5, Ri6, R[7, R[8, R[9, identical or different, represent

[0242] - a hydrogen atom,

[0243] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0244] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0245] - a phenyl.

[0246] In another variant of this embodiment, R20, R21, R22, R23, R24, R25, and R26, identical or different, represent

[0247] - a hydrogen atom,

[0248] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0249] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0250] - a phenyl.

[0251] According to a twentieth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0252] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0253] with R2, R3, R4, R5, R6, R?, and R8, representing a hydrogen atom;

[0254] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0255] with Rn, Ru, R[5, R[6, Rn, R[8, Ri9, representing a hydrogen atom;

[0256] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0257] with R2o, R21, R22, R23, R24, R25, R26, representing hydrogen atom,

[0258] D and D' represent a carbonyl (C=O).

[0259] According to a twenty-first embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0260] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0261] with R2, R3, R4, R5, R6, R?, and R8, representing a hydrogen atom;

[0262] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0263] with Rn, R[5, R[6, R[8, Ri9, representing a hydrogen atom, and Ru, Rn, representing a phenyl;

[0264] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0265] with R20, R22, R23, R23, and R26, representing a hydrogen atom,

[0266] R2i, R24, represents a phenyl, and

[0267] D and D' represent a carbonyl (C=O).

[0268] According to a twenty-second embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0269] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0270] with Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R[2, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0271] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0272] with Rn, Ru, R[5, R[6, Rn, Ri8, Ri9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0273] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0274] with

[0275] R2o, R2i, R22, R23, R24, R25, R26, identical or different, representing an atom of hydrogen, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being possibly substituted,

[0276] D and D' represent a carbonyl (C=O), and

[0277] T' representing O.

[0278] According to a twenty-third embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0279] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0280] with RB R2, R3, R4, R5, R6, R7, R8, R9, R10, Ru and Rn, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0281] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0282] with Rn, Ru, R[5, R[6, Rn, Ri8, Ri9, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0283] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0284] with

[0285] R2o, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising from 6 to 10 carbon atoms,

[0286] D and D' represent a carbonyl (C=O), and

[0287] T' representing O.

[0288] In a variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru and R12, identical or different,

[0289] represent

[0290] - a hydrogen atom,

[0291] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0292] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0293] - a phenyl.

[0294] In another variant of this embodiment, R13, R14, R15, R16, R17, R18, R19, identical or different, represent

[0295] - a hydrogen atom,

[0296] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0297] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0298] - a phenyl.

[0299] In another variation of this embodiment, R20, R21, R22, R23, R24- R25, and R26, identical or different, represent

[0300] - a hydrogen atom,

[0301] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0302] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0303] - a phenyl.

[0304] According to a twenty-fourth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0305] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by with Rb R2, R2, R4, R5, Rg, R7, R$, R9, Rio, Ru and Ri2, representing a hydrogen atom;

[0306] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0307] with

[0308] Rn, Ru, R15, Ri6, R17, Ri8, R19, representing a hydrogen atom,

[0309] or

[0310] Rn, R15, Ri6, Ri8, R19, representing a hydrogen atom, and

[0311] Ru, Rn, representing a phenyl;

[0312] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0313] R2o, R2i, R22, R23, R24, R25, and R26, represent a hydrogen atom,

[0314] T' represents O, and

[0315] D and D' represent a carbonyl (C=O).

[0316] According to a twenty-fifth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0317] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0318] with RB R2, R3, R4, R5, R6, R7, R8, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0319] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0320] with Rn, R[4, Ri5, Ri6, Rn, R[8, R[9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted;

[0321] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0322] with

[0323] R2o, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted,

[0324] D and D' represent a carbonyl (C=O), and

[0325] T' representing O.

[0326] According to a twenty-sixth embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0327] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0328] with

[0329] Rb R2, R3, R4, R5, R6, R7, and R8, identical or different, represent a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0330] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0331] with

[0332] Rn, Ru, R15, Ri6, Rn, Ri8, R19, identical or different, representing a hydrogen atom, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 6 carbon atoms, an aryl radical comprising 6 to 10 carbon atoms;

[0333] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0334] with

[0335] R2o, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 8 carbon atoms, for example 1 to 6 carbon atoms, an aryl radical comprising from 6 to 10 carbon atoms,

[0336] D and D' represent a carbonyl (C=O), and

[0337] T' representing O.

[0338] In a variant of this embodiment, Rb R2, R3, R4, R5, R6, R7, and R8, identical or different,

[0339] represent

[0340] - a hydrogen atom,

[0341] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0342] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0343] - a phenyl.

[0344] In another variant of this embodiment, Rn, RM, R[5, R[6, Rn, R[8, R19, identical or different, represent

[0345] - a hydrogen atom,

[0346] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0347] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0348] - a phenyl.

[0349] In another variant of this embodiment, R20, R2i, R22, R23, R24, R25, and R26, identical or different, represent

[0350] - a hydrogen atom,

[0351] - an alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers,

[0352] - an alkoxy group whose alkyl group is chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, and their branched isomers,

[0353] - a phenyl.

[0354] According to a twenty-seventh embodiment of the invention, the molecule of formula (I) as defined above, is characterized in that

[0355] - E and E', together with the carbon atoms to which they are bonded, form a heterocycle comprising 8 members chosen from the group formed by

[0356] with

[0357] Rb R2, R3, R4, R5, R6, R7, and R8, identical or different, represent a hydrogen atom;

[0358] - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0359] with Rn, Ru, R[5, R[6, Rn, R[8, Ri9, representing a hydrogen atom,

[0360] or

[0361] Rn, R15, Rie, Ri8, Ri9, representing a hydrogen atom, and

[0362] Rm, Rn, representing a phenyl;

[0363] - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

[0364] R2o, R21, R22, R23, R24, R25, and R26, represent a hydrogen atom,

[0365] T' represents O, and

[0366] D and D' represent a carbonyl (C=O).

[0367] According to a twenty-eighth embodiment of the invention, the molecule of formula (I) are chosen from the group formed by

[0368] (S)-BN-(P / M)-Helicene 1 BP-(P / M)-Helicene 2

[0369] BP-(rac)-Helicene 3 (P)-BN-(P / M)-Helicene 4

[0370]

[0371] BP-(rac)-Helicene 5

[0372] The molecules of formula (I) of the invention can be prepared as described below. A) Description of the synthesis of symmetrical heterohelicenes helicenes 1-3 ([Fig.4])

[0373] In a first step the precursors noted B are formed by applying the synthesis described in J. Am. Chem. Soc. 2016, 138, 3990 with the BINOL motif, to the biphenol motif) via a monotope sequence (in one pot) then the reaction crude is purified on silica gel. The target molecules helicenes 1-3 are then obtained by a first cyclization step in triflic acid (CF3SO3H) at room temperature (20 ± 5°C) to give an intermediate compound carrying imine functions (C=NH, after washing in basic medium) followed by a hydrolysis step of these imines in an aqueous HCl / dioxane mixture (to lead to the ketone function, C=O) at 95°C (unusual temperature for this type of hydrolysis but necessary to obtain the products).The reaction crude is then purified on silica gel to give a mixture of diastereoisomers in the case of the presence of a BINOL motif) as shown in [Fig.4], or a racemic mixture in . the case of the presence of a biphenol motif (,f'%)• Subsequently, the enantiomers or the diastereoisomers are purified by chiral preparative HPLC to obtain optically pure molecules.

[0374] B) Description of the synthesis of non-symmetric heterohelicenes helicenes 4-5 ( [Fig.5])

[0375] In a first step, the precursors denoted D (structure described by; Xu Bingjia et al. (CN107629785) are formed in two steps. The target molecules are obtained in a similar manner as for the symmetrical heterohelicenes. In the case of the molecules having a BINOL motif ([Fig.5])) the two diastereoisomers formed can be separated on silica gel, which is a strong point of the process of the invention because, in general, obtaining optically pure (hetero)helicenes requires purification by chiral preparative HPLC. In the case of molecules having a 2,2'-Biphenol motif, the enantiomers are purified by chiral preparative HPLC.

[0376] Thus, the molecules of formula (I) have the advantage of being able to be synthesized in a few steps ([Fig.5]), involving reactions that are fairly simple to implement (no transition metals, basic building blocks commercially available). They are therefore potentially synthesizable on a large scale.

[0377] The synthetic routes of molecules 1-3 and 4-5 as described above are suitable for the synthesis of other molecules of formula (I).

[0378] Those skilled in the art are able to transpose and adapt the synthesis routes of symmetrical and non-symmetrical heterohelicenes described above to other molecules of formula (I).

[0379] The main advantages of the methods for synthesizing molecules of formula (I) are as follows:

[0380] 1) simple synthetic access (1 to 3 synthesis steps involving products commercially available starting materials) for this type of molecule and even in the case of the construction of non-symmetrical (hetero)helicenic motifs which are generally difficult to access;

[0381] 2) the possibility of purifying optically pure molecules on silica gel (diastereoisomers) obtained when one of the starting bricks is an enantiopure chiral compound (BINOL) whereas in general helicenes are synthesized in racemic form (mixture of two 50 / 50 enantiomers).

[0382] The molecules of the invention possess remarkable properties, in particular:

[0383] - a very high quantum yield (up to 86% in solution in the dichloromethane) which is quite rare for helical molecules combined with delayed fluorescence emission properties (TADF),

[0384] - delayed fluorescence emission (TADF) theoretically allowing the collection all excitons formed in the emitting layer of OLEDs by the recombination of the electron-hole pair),

[0385] - chiroptical properties: electronic circular dichroism (ECD) and light circularly polarized (CPL), and

[0386] - good solubility in organic solvents.

[0387] Photophysical and chiroptical studies of the optically pure molecules of the invention have made it possible to highlight:

[0388] 1) excellent performance in terms of fluorescence emission (wavelength emission centered around 540 nm for compounds 1-3 and 600-610 nm for compounds of type 4-5 in solution in dichloromethane) with quantum yields (O,) up to 86% in solution in dichloromethane;

[0389] 2) interesting chiroptical properties with asymmetry factors in absorption (gabs) up to 1.2 x 10 2 and emission of circularly polarized light with emission asymmetry factors between 0.5 and 1.5 x 103 in solution in dichloromethane;

[0390] 3) the emission of TADF with long lifetimes between 200 and 600 ps and low AEst (around 0.300 eV) well compatible with the possibility of emitting delayed fluorescence in solution in 2-methyltetrahydrofuran. In toluene, the quantum yields obtained for degassed solutions are higher than the quantum yields of molecules in a non-degassed solution.

[0391] Some of these molecules have been incorporated into OLED devices with external quantum efficiencies greater than 5% confirming the participation of excitons in the triplet state (due to the TADF property).

[0392] The properties of these molecules and their advantages in terms of application are recorded in the following table:

[0393] [Tables 1] Property(s) Application TADF Dopant for the emitting layers of OLEDs; Fluorescent probes with a long lifetime (time-resolved fluorescence (TRF)); organic photocatalysts TADF + CPL Dopant in the emitting layers of circularly polarized light-emitting OLEDs (CP-OLED); chiral photocatalysts

[0394] The molecules of formula (I) according to the invention therefore make it possible to simultaneously combine the properties of circularly polarized light emission (CPL) and those of delayed fluorescence (TADF). The combination of these properties within the same compound has strong potential for application as a dopant in the emitting layers of organic light-emitting diodes (OLEDs). In addition, these compounds could also find applications in the field of photocatalysis.

[0395] The subject of the invention is therefore the use of a molecule of formula (I) according to the invention as a photocatalyst, in particular in reactions for activating CH bonds, reactions for forming CC and CY bonds with Y being a heteroatom, or as a dopant, in particular in the emitting layers of organic light-emitting diodes (OLEDs).

[0396] The invention further relates to an electroluminescent device or a light-emitting diode comprising a molecule of formula (I) according to the invention. EXAMPLES

[0397] All commercial reagents, purchased from Aldrich and Alpha Aesar, were used without purification. The progress of the reactions was monitored by thin-layer chromatography on pre-coated Merck silica gel plates (60F-254). Visualization was performed by UV light (254, 365 nm). 1H NMR (400 MHz) and 13C NMR (101 MHz) spectra were recorded on a Bruker Avance 400 MHz spectrometer. Chemical shifts are indicated in parts per million (ppm) downstream of the residual solvent peaks and coupling constants are indicated in Hertz (Hz). Splitting patterns are designated as singlet (s), doublet (d), triplet (t). Splitting patterns that could not be interpreted or easily visualized are designated as multiplet (m).

[0398] Mass spectra were performed by high-resolution mass spectrometry (HRMS) on a Waters Xevo® G2-XS spectrometer.

[0399] UV-visible spectra were recorded on a JASCO V-750 spectrometer using a 10 mm path quartz cell.

[0400] Circular dichroism (CD) spectra were recorded on a Jasco J-815 spectropolarimeter equipped with a Peltier thermostatted cell holder and a Xe laser. Data were recorded at 20°C using a 1 mm x 1 cm cell. The obtained signals were processed by subtracting the contribution of the solvent and cells.

[0401] Emission spectra and TCSPC experiments were performed on an Edinburgh FS-5 spectrofluorimeter using the SC-20 module. Absolute fluorescence quantum yields for solutions were determined using an integrating sphere (Edinburgh SC-30).

[0402] Circularly polarized luminescence (CPL) measurements were performed using a commercially available JASCO CPL-300 instrument at room temperature (20+5 °C) in a 10 x 10 mm cell. The excitation wavelength and instrument parameters were adapted for each sample. The displayed spectra are the average values ​​of a minimum of 10 accumulations. Circular dichroism (CD) spectra were recorded on a Jasco spectropolarimeter (model J-815) equipped with a Peltier thermostatted cell holder and a Xe laser. Data were recorded at 20 °C using a 1 mm x 1 cm cell. The obtained signals were processed by subtracting the contribution of the solvent and the cells.

[0403] Circularly Polarized Luminescence or CPL measurements (general):

[0404]

[0405]

[0406]

[0407]

[0408]

[0409]

[0410]

[0411]

[0412] A molecule can preferentially absorb circularly polarized light, in the same way, it can also emit an excess of circularly polarized light by radiative de-excitation in the form of luminescence (fluorescence, delayed fluorescence or phosphorescence). To observe this phenomenon of circularly polarized luminescence (called CPL for Circularly Polarized Luminescence), the fluorophore must be subjected to a force field: it can come from the chiral fluorochrome studied (chiral force field intrinsic to the molecule), we then speak of CPL, or it can come from an external magnetic field which is in the direction of propagation of the emitted light, in this case, the molecule studied is not necessarily chiral and we speak of MCPL (for Magnetic Circularly Polarized Luminescence). In the context of the present invention, only CPL will be studied; no study will be carried out on the properties of MCPL. As for circular dichroism, to measure the CPL we measure the difference in intensity ( AZ(2)) between the emission of left circularly polarized light (Z ( 2 ) j P31 ratio to the emission of right circularly polarized light: AZ(2) measurements are quite complex since they can be subject to numerous experimental artifacts (linearly polarized light, birefringence phenomena) and to a problem related to the detection limit. Indeed, in general, the proportion of circularly polarized light is very low compared to the total emitted light Z(2), therefore the photomultipliers used must be very efficient. In order to compare the emission of circularly polarized light between fluorophores, the luminescence asymmetry factor should be used: Wil= 2 w where I(A) represents the total luminescence intensity. Due to the "factor 2", the ^lum can take values ​​between -2 and 2, as for the Subsj representing a total emission of right or left circularly polarized light. In the same way as for the CD, if the value of Slum is zero, then the molecule does not emit an excess of circularly polarized light. CPL measurements provide information on the chiral environments of transitions associated with radiative de-excitations of compounds and therefore of the lower energy singlet or triplet states which are responsible for fluorescence (delayed or not) and phosphorescence. However, during the phenomenon of absorption and internal conversion (and intersystem crossing for phosphorescence), it Sometimes the molecule changes geometry relative to its ground state. This is why it is possible to have a Sabs other than 0 and a zero Slum (and theoretically the reverse is also possible, but has never been observed). A loss of chiral information can occur if the geometry of the molecule is modified, and if the radiative de-excitation transition does not involve the intrinsically chiral parts of the molecule.

[0413] It is also possible to determine theoretically, that is to say by modeling and calculations, the values ​​of Slutn via the following formula:

[0414] e) - ^Re[ ] - AcmB-^- *

[0415] In this formula and m represent respectively the electric and magnetic dipole transition moments in the excited state, & is the angle between these two vectors.

[0416] With this formula, it is easy to understand that the higher the values ​​of the norms of the vectors are large, the higher the value of 8lutn will be (if B j )• Notwithstanding, in practice m is often very small compared to (hence the approximation „ ( ^ ) ~ 4cosB~ ), so the 8lum is directly proportional to I m I and vice versa proportional to Therefore, high values ​​of 8lum are expected for magnetically allowed and electrically forbidden transitions. This is why CPL measurements were mainly applied to lanthanide complexes at first. These compounds have the particularity of being able to carry out particular transitions (f - f Laporte transition, theoretically forbidden, but observable thanks to spin-orbit coupling) which give a very large magnetic transition moment and a small electrical transition moment. This is why, despite the high Slum values ​​obtained (the maximum value measured so far is 1.38), the quantum yields of this type of complex are low (of the order of a few percent in the best cases). Delayed fluorescence Reverse Intersystem Crossing (rISC)

[0417] As mentioned previously, from the Ti state it is possible for a molecule to return to an excited singlet state Si. This can be done by triplet-triplet annihilation or by intersystem crossing. In the second case, if the energy difference between the lowest energy singlet state Si and the lowest energy triplet state Tj (AEst) is small enough, we speak of reverse intersystem crossing (rISC), we then have the following transition: Ti^Sp

[0418] Like intersystem crossing, reverse intersystem crossing can only take place if the initial state (Ti) has a sufficiently long lifetime and the speed of reverse intersystem crossing is sufficiently high.

[0419] This phenomenon is energetically dependent since we pass from a low energy state (TJ) to a higher energy state (Si). Thus, it is considered that for there to be spontaneous, at room temperature (20 s 5°C), reverse intersystem crossing, the energy difference between Si and Ti must be less than 500 meV: A Est < 500 nwV. This value is often debated because it depends on the fluorophore studied: The limit value of 360 meV is also found in the literature.

[0420] The A EST is directly proportional to the orbital overlap between the HOMO and the LUMO of a molecule. Thus, the greater the separation between these two orbitals, the lower the value of A EST will be. The challenge of a molecular design to have a significant intersystem crossing lies in obtaining a good spatial separation of these frontier orbitals. Various molecular designs have been developed to meet these conditions, the most commonly used involving donor-acceptor type fluorophores, where these two units form a dihedral angle as close as possible to 90 0 . This makes it possible to position the HOMO predominantly on the donor group and the LUMO predominantly on the acceptor. However, care must be taken not to completely separate the two frontier orbitals because the quantum yield is proportional to the orbital overlap between the HOMO and the LUMO.It is therefore necessary to find a compromise between a good separation to minimize the A EST and maintain interesting quantum yields.

[0421] Thermally activated delayed fluorescence After the reverse intersystem crossing, the molecule returns to the Sp state. From then on, it is possible for it to emit fluorescence (de-excitation Si—>S0) which will have the same emission wavelength as the prompt fluorescence. However, as the molecule has passed through several states, the lifetime of this fluorescence is different, it is longer, of the order of 108 to 105 seconds, which is why this phenomenon is called "delayed fluorescence".

[0422] However, the term "delayed fluorescence" used in French omits an important part of the phenomenon. Indeed, in English, delayed fluorescence is called "Therally Activated Delayed Fluorescence" (abbreviated TADF), which could be translated as: "thermally activated delayed fluorescence". Because of the inverse intersystem crossing, which is a temperature-dependent process, delayed fluorescence is also temperature-dependent. Thus, the higher the temperature of the medium, the more intersystem crossing will be favored, and the more molecules will be able to return to the Si state to emit delayed fluorescence. Quantum efficiency

[0423] The quantum efficiency, which measures the efficiency of photon emission, is calculated relatively to a suitable reference whose absorbance spectra and fluorescence overlap with those of the compound studied. The formula used is as follows:

[0425] where S represents the area under the emission curve of the compound to be studied and Sref the area under the emission curve of the reference, A and Aref the absorbances of the compound to be studied and of the reference respectively, n and nref are the refractive indices of the media in which the molecule of interest and the reference are found. Finally (Pref is the quantum yield of the reference. Photophysical data and TADF#:

[0426] To demonstrate the TADF properties of the compounds of the invention, it is necessary - to verify that the fluorescence decline is biexponential: short lifetime of the order of a nanosecond and a long lifetime in degassed solution (the oxygen in the air quenches the triplet state), and - look at whether an increase in quantum efficiency ( <bf) est observé entre la solution à l’air et dégazée l’argon.

[0427] Example 1: General process for the synthesis of symmetrical heterohelicenes according to the invention (procedure A) Imine intermediate loti 6M HCI / 1,4-dioxane 95°C, 24 h (S^BN^Mf'J-helicene 1 diastereomeric ratio 37:63 (MP)

[0428] In a 10 ml round bottom flask, containing (S)-BNTPNCz2 (400 mg, 0.54 mmol), 1.5 ml of sulfonic acid or TfOH or CF3SO3H is added. The dark blue reaction mixture is stirred at room temperature (20 ± 5°C) for 12 h. Then, crushed ice is added to the reaction mixture and a blue precipitate is collected by filtration and washed with distilled water. The precipitate is dissolved in dichloromethane or DCM (200 ml). The resulting organic phase is then washed with 100 ml of 1 M NaOH solution. The color of the organic phase then changes from dark blue to yellow. The aqueous phase is extracted again with DCM (100 ml). The collected organic phase is dried over anhydrous Na2SO4 and filtered, then concentrated in vacuo. The crude product (Int 1) obtained as a yellow solid is analyzed by 1H NMR ([Fig.3a]). The product obtained can be used for the next step without further purification.

[0429] In a 50 mL round-bottom flask, the intermediate imine Intl (395 mg, 0.54 mmol) is solubilized in dioxane (15 mL). Then, 15 mL of 6 M HCl is added. The reaction mixture is stirred at 95°C for 24 hours and then cooled to room temperature. The reaction mixture is diluted with DCM (200 mL) and then washed with 150 mL of 2 M NaOH solution. The aqueous phase is extracted again with DCM (200 mL). The collected organic phase is then dried over anhydrous Na2SO4, filtered, and then concentrated in vacuo. The crude product is purified by silica gel chromatography using a DCM / heptane mixture (80 / 20) as eluent. The product is obtained as an orange solid (291 mg, 72%). The crude reaction mixture analyzed by *H NMR spectrum is presented in [Fig.3b].

[0430] This is a mixture of diastereoisomers ((Sj-BN-^j-Helicene 1 and (S)-BN-(P)-Helicene 1. *H NMR and HPLC analyses show that these diastereoisomers are formed in a ratio of 37:63 (M:P). The diastereoisomers can be separated by chiral HPLC.

[0431] Column: Xselect HSSC18 (250 x 21.2 mm, 5 pm); Flow rate: 65 mL / min; Temperature: 40°C; Pressure: 120 bar; Detection: UV 200-400 nm Max Abs; Solvent: A (CO2), B (MeOH). Gradient: 30% A, 40% B, 12 min; 70% A, 30% B. (see HPLC section below Page no. 13).

[0432] BP-(rac)-Helicene 2 is synthesized according to general procedure A and the reaction was carried out on a 0.78 mmol (500 mg) scale. The product (racemic mixture) is isolated as an orange solid (225 mg, 45%) by silica gel chromatography using ethyl acetate / heptane 10:90 (v / v) as eluent.

[0433] The enantiomers are separated by chiral HPLC.

[0434] Column: CHIRALPAK IA (250 x 30 mm, 5 pm); Flow rate: 70 mL / min; Temperature: 40°C; Pressure: 120 bar; Detection: UV 200-400 nm Max Abs; Solvent: A (CO2), B (DCM). Gradient: Isocratic 60% A, 40% B.

[0435] BP-(rac)-Helicene 3 is synthesized according to general procedure A and the reaction was carried out on a scale of 0.53 mmol (500 mg). The product (racemic mixture) is isolated as a red solid (150 mg, 30%) by column chromatography using silica gel and an ethyl acetate / cyclohexane mixture (14 / 86) as eluent.

[0436] Example 2: General process for the synthesis of non-symmetrical heterohelicene (procedure B) WBNTPNPhenexCz Intermediate irnine helicénrs Ittf 2 6M MCI / WdioxaTO 95 24 h V (JîJ-BN-tFZtfhhéHcène 4

[0437] In a 10 ml round bottom flask, containing (R)-BNTPNPhenoxCz (500 mg, 0.66 mmol) 1.5 ml of TfOH are added. The dark blue reaction mixture is stirred at room temperature (20 ± 5°C) for 24 h. Then, crushed ice is added to the reaction mixture and the blue precipitate formed is collected by filtration and washed with distilled water. The blue precipitate is then dissolved in DCM (200 ml) and the resulting organic phase is washed with 100 ml of 1 M NaOH solution. The aqueous phase is again extracted with DCM (100 ml). The organic phase is then dried over anhydrous Na2SO4 and filtered, then concentrated in vacuo. The crude product obtained (Int 2) in the form of a brown solid is analyzed by 'H NMR. The product can be used for the next step without further purification.

[0438] In a 50 mL round-bottomed flask, the intermediate imine Int 2 (470 mg, 0.62 mmol) is solubilized in dioxane (20 mL). Then, 20 mL of 6 M HCl is added and the color of the solution changes from yellow to blue. The reaction mixture is stirred at 95°C for 24 hours and then the reaction mixture is cooled to room temperature. The color of the reaction mixture then changes from blue to red. The mixture The reaction mixture is diluted with DCM (250 ml) and the resulting aqueous phase is washed with 200 ml of 2M NaOH solution. The aqueous phase is extracted again with DCM (250 ml). The organic phase is then dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The crude product is purified by silica gel chromatography using a DCM / heptane mixture (90 / 10) as eluent.

[0439] Here, the diastereoisomers are separated by silica gel chromatography using a DCM / Heptane (90 / 10) mixture as eluent. The products are obtained in the form of red solids (R)-BN-(M)-Helicene 4 (42 mg, 7.9%), (R)-BN-(P)-Helicene 4 (44 mg, 8.3%) and a mixture of the two diastereoisomers (30 mg, 5.7%).

[0440] BP-(rac)-Helicene 5 is synthesized according to general procedure B and the reaction was carried out on a scale of 0.76 mmol (500 mg). The products (racemic mixture) are isolated as a red solid (70 mg, 14%) by silica gel chromatography using ethyl acetate / heptane (8 / 92) as eluent.

[0441] The enantiomers are separated by chiral HPLC.

[0442] Column: CHIRALPAK IB (250 x 4.6 mm, 5 pm); Flow rate: 4 mL / min; Temperature: 40°C; Pressure: 120 bar; Detection: UV 200-400 nm Max Abs; Solvent: A (CO2), B (IPA: DCM). Gradient: Isocratic 70% A (CO2), 30% B (20% IPA: 10% DCM).

[0443] NMR characterization data of the heterohelicenes according to the invention, synthesized according to example 1 or example 2:

[0444] (S)-BN-(M)-Helicene 1

[0445] 1 H NMR (400 MHz, CDC13) ô 8.48 (d, J = 7.8 Hz, 2H), 8.33 (d, J = 7.3 Hz, 2H), 7.84 (dd, J = 8.0, 5.2 Hz, 6H), 7.71 (t, J = 7.6 Hz, 2H), 7.66 - 7.62 (m, 4H), 7.41 (t, J = 7.3 Hz, 2H), 7.33 (t, J = 7.5 Hz, 2H), 6.96 (t, J = 7.5 Hz, 2H), 6.65 (t, J = 7.8 Hz, 2H), 6.17 (d, J = 8.4 Hz, 2H).

[0446] 13 C NMR (151 MHz, CDC13) ô 177.36, 151.04, 147.23, 139.42, 137.77, 132.34, 132.02, 130.68, 128.41, 127.33, 127.03, 126.58, 126.18, 126.04, 125.47, 124.87, 124.83, 124.58, 123.30, 123.00, 121.42, 121.37, 121.19, 112.19.

[0447] HRMS [ESI] :m / z calculated for M = C52H26N2O4

[0448] Calculated (M+Na)+ 765.1791, Found 765.1790.

[0449] (S)-BN-(P)-Helicene 1

[0450] RMN 1 H (400 MHz, CDC13) ô 8.41 (d, J = 7.9 Hz, 2H), 8.28 (d, J = 7.4 Hz, 2H), 7.95 (d, J = 8.8 Hz, 2H), 7.82H), (7.82H), (7.82H). = 7.7 Hz, 2H), 7.65 (dd, J = 12.8, 5.1 Hz, 4H), 7.41 (t, J= 7.3 Hz, 2H), 7.33 (t, J= 7.4 Hz, 2H), 6.96 (t, J=6, 7. 7 (H6), Hz, 2H), 6.21 (d, J = 8.5 Hz, 2H).

[0451] NMR at 13 C (151 MHz, CDC13) at 177.65, 151.11, 146.49, 139.33, 137.58, 132.10, 130.93, 128.46.4, 16.27. 126.08, 125.53, 124.83, 124.66, 124.48, 124.13, 123.72, 123.44, 121.82, 121.20, 191.03,

[0452] HRMS [ESI] :m / z calculated for M = C52H26N2O4

[0453] Calculated (M+H)+ 743.1791, Found 765.1790.

[0454] BP-(rac)-Helicene 2

[0455] RMN 1 H (400 MHz, CDC13) ô 8.51 (d, J = 7.7 Hz, 2H), 8.38 (d, J = 7.2 Hz, 2H), 7.91 (d, J = 7.7 Hz, 2H), 7.7, 75 (t (d, J= 8.3 Hz, 2H), 7.56 (dd, J = 7.5, 1.6 Hz, 2H), 7.43 (ddd, J = 7.2, 6.6, 1.7 Hz, 2H), 7.36 (dd, J= 10.7, 0,2.2 Hz), 2H), 6.78 - 6.72 (m, 2H), 6.30 (d, J = 8.6 Hz, 2H).

[0456] NMR at 13 C (151 MHz, CDC13) at 177.50, 153.28, 139.40, 137.68, 132.78, 129.99, 128.45, 127.00, 129.00, 124.69, 124.46, 123.23, 122.49, 121.20, 112.28.

[0457] HRMS [ESI] :m / z calculated for M = C 44 H 22 N 2 O 4

[0458] Calculated (M+H)+ 643.1656, Found 643.1658.

[0459] BP-(rac)-Helicene 3

[0460] RMN 1 H (400 MHz, CD2C12) ô 8.62 (d, J = 3.3 Hz, 4H), 8.14 (d, J = 1.5 Hz, 2H), 7.81 (d, J = 7.4 Hz, 4H), 7.5H - 7.58 J = 7.5, 1.6 Hz, 2H), 7.50 (t, J = 7.6 Hz, 4H), 7.44 - 7.31 (m, 10H), 7.27 (t, J = 7.5 Hz, 4H), 7.22 - 7.87 (dd, 2H), J = 9 Hz, 2H), 6.41 (d, J = 8.7 Hz, 2H).

[0461] 13 C NMR (101 MHz, CD2C12) or 177.23, 153.66, 140.93, 140.62, 139.54, 138.46, 137.87, 136.392.72, 131.82. 129.14, 128.60, 128.13, 127.98, 127.62, 127.32, 125.89, 125.23, 123.37, 171.94.

[0462] HRMS [ESI] :m / z calculated for M = C 68 H38 N 2 O 4

[0463] Calculated (M+H)+ 947.2910, Found 947.2914 .

[0464] (Æ)-BN-(M)-Helicene 4

[0465] RMN 1 H (400 MHz, CD2C12) ô 8.27 (d, J= 7.8 Hz, 1H), 8.18 (d, J= 7.4 Hz, 1H), 7.93 (ddd, J= 31.1, 15.8, J = 6.9), Hz, 1H), 7.59 (dt, J= 11.9, 8.0 Hz, 4H), 7.50 - 7.28 (m, 8H), 7.21 (t, J = 7.4 Hz, 1H), 6.56 - 6.43 (m. 5. 2H), 6.56 (d, J= 8.0 Hz, 1H).

[0466] 13 C NMR (101 MHz, CD2C12) at 177.38, 132.40, 132.34, 132.19, 131.07, 130.99, 128.82, 128.78, 128.25, 127.56, 127.42, 1247.09, 127.4, 127.06. 126.03, 125.93, 125.87, 125.73, 125.58, 125.43, 124.49, 123.64, 123.59, 123.39, 122.88, 122.24, 121.58, 121.50, 121.25, 121.19, 119.55, 116.51, 114.68, 114.60.

[0467] HRMS [ESI] :m / z calculated for M = C52H26N2O5

[0468] Calculated (M+H)+ 759.1920, Found 759.1917.

[0469] (Æ)-BN-(P)-Helicene 4

[0470] RMN 1 H (400 MHz, CD2C12) ô 8.25 (d, 7 = 7.8 Hz, 1H), 8.12 (d, J = IA Hz, 1H), 8.03 (d, J= 8.9 Hz, 1H), 7.98 (dd, J= 7.4, 1.9 Hz, 1H), 7.96 - 7.92 (m, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.83 (d, J= 8.8 Hz, 1H), 7.74 (d, J= 7.5 Hz, 1H), 7.63 (dd, J= 8.3, 2.3 Hz, 2H), 7.56 - 7.25 (m, 10H), 7.16 (t, J= 7.3 Hz, 1H), 6.50-6.41 (m, 2H), 5.97 (dd, J= 10.2, 4.3 Hz, 1H), 5.72 (d, J= 8.0 Hz, 1H).

[0471] RMN 13 C (101 MHz, CD2C12) ô 177.33, 176.29, 151.43, 151.19, 147.25, 147.01, 146.60, 145.64, 138.48, 138.00, 132.69, 132.42, 132.33, 132.25, 131.28, 131.17, 128.87, 128.84, 127.95, 127.42, 127.23, 127.21, 127.00, 126.50, 126.25, 126.11, 125.96, 125.84, 125.78, 125.49, 125.26, 125.20, 124.35, 124.31, 123.51, 123.44, 123.29, 122.92, 122.77, 122.23, 121.67, 121.51, 121.16, 120.77, 119.51, 116.50, 114.59, 114.55.

[0472] HRMS [ESI] :m / z calculé pour M = C52H26N2OS

[0473] Calculated (M+H)+ 759.1920, Found 759.1921.

[0474] BP-(rac)-Helicene 5

[0475] 1 H NMR (400 MHz, CD2C12) ô 8.26 (d, J = 7.4 Hz, 1H), 8.14 (d, J = 7.3 Hz, 1H), 7.97 (dd, J = 7.2, 2.0 Hz, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.60 - 7.50 (m, 4H), 7.44 (d, J = 8.3 Hz, 2H), 7.38 - 7.25 (m, 7H), 7.18 (t, J = 7.2 Hz, 1H), 6.50 - 6.42 (m, 2H), 5.98 (ddd, J = 8.6, 6.3, 2.6 Hz, 1H), 5.70 (d, J = 8.1 Hz, 1H).

[0476] 13 C NMR (101 MHz, CD2C12) ô 177.29, 176.27, 153.58, 153.48, 147.31, 147.09, 138.59, 138.14, 133.02, 132.81, 130.26, 130.17, 128.69, 128.63, 128.09, 127.49, 126.55, 125.97, 125.86, 125.82, 125.51, 125.26, 124.33, 124.31, 123.51, 123.34, 122.82, 122.37, 121.48, 121.16, 120.87, 119.53, 116.50, 114.62, 114.56.

[0477] HRMS [ESI]: m / z calculated for M = C 44 H 22 N 2 O 5

[0478] Calculated (M+Na)+ 681.1426, Found 681.1426. < / t>

Claims

1. Claims Molecule of formula (I) In which: - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by with Rb R2, R3, R4, R5, R6, R7, Rs, R% Rio, R11 and R12, identical or different, representing a hydrogen atom, a halogen atom chosen from F, Cl, Br and I, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted; - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with Rn, Ru, R15, Rie, Rn, Ris, Rw, R31, R32, R33 and R34, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D representing a carbonyl (C=O), an imine of formula C=NH or C=NCH3, an iminium of formula C=NH2+ or C=NHCH3+, and T representing a heteroatom chosen from the group formed by O, S, and CRRq with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, L representing a heteroatom chosen from the group formed by O and S; - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with R20, R21, R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group in which the alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D' representing a carbonyl (C=O), and T' representing a heteroatom chosen from the group formed by O, S, and CR'R'o with R' and R'o, identical or different, representing

2. a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, and L' representing a heteroatom chosen from the group formed by O and S; \ represents the point of attachment of the atoms to the rest of the molecule by a covalent bond. Molecule according to claim 1, characterized in that - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by with Ri, R2, R3, R4, R5, Re, R7, Rs, R9, Rio, Ru and R[2, identical or different, representing a hydrogen atom, a halogen atom chosen from F, Cl, Br and I, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising

3. from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted. Molecule according to one of claims 1 or 2, characterized in that that - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

4. with Rn, Ru, Rb, Ri6, Rn, Ri8, Ri9, R3i, R32, R33 and R34, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D representing a carbonyl (C=O), and L representing a heteroatom chosen from the group formed by O and S. Molecule according to one of claims 1 or 2, characterized in that - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

5. with Rn, Ru, Rb, Rie, Rn, Ris, Rw, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D representing a carbonyl (C=O), and T representing a heteroatom chosen from the group formed by O, S, and CRRq with R and Ro, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted. Molecule according to any one of claims 1 to 4, characterized in that - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

6. with R20, R21» R22, R23, R24, R25, R26, R27, R28, R29 and R30, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group in which the alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D' representing a carbonyl (C=O), and The representing a heteroatom chosen from the group formed by O and S. Molecule according to any one of claims 1 to 4, characterized in that - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

7. with R20, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, D' representing a carbonyl (C=O), and T' representing a heteroatom chosen from the group formed by O, S, and CR'R'o with R' and R'o, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted. Molecule according to claim 1, characterized in that - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by with Ri, R2, R3, R4, R5, R6, R7, R8, R% Rio, R11 and R12, identical or different, representing a hydrogen atom, a halogen atom chosen from F, Cl, Br and I, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted; - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with R13, Rm, R15, R16, R17, R18, R19, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

8. with R20, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted. Molecule according to claim 1, characterized in that - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by R; Ry with Ri, R2, R3, R4, R5, R6, R7, R8, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted; - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with Rn, RM, R[5, R[6, Rn, R[8, R19, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

9. with R2o, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an alkoxy group whose alkyl group comprises 1 to 8 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted. Molecule according to claim 1, characterized in that - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by with Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, R11 and R[2, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted; - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with Rn, R[4, Ri5, Ri6, R[7, R[8, R[9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by

10. with R2o, R21, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, and T' representing O. Molecule according to claim 1, characterized in that - E and E', together with the carbon atoms to which they are bonded, form an 8-membered heterocycle chosen from the group formed by with Ri, R2, R3, R4, R5, R6, R7, Rs, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted; - A and A', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with Rn, R[4, Ri5, Ri6, R[7, R[8, R[9, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an alkoxy group whose alkyl group contains 1 to 8 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, - X and X', together with the carbon atoms to which they are bonded, form a 6-membered heterocycle chosen from the group formed by with R2o, R2i, R22, R23, R24, R25, R26, identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, the alkyl and aryl radicals being optionally substituted, and T' representing O.

11. Molecule according to any one of claims 1 to 10, characterized in that it is chosen from the group formed by

11. (5)-BN-(P / M)-Helicene 1 BP-(P / M)-Helicene 2 BP-(P / M)-Helicene 3 (R)-BN-(P / M)-Helicene 4

12.

13. BP-(P / M)-Helicene 5 Use of a compound of formula (I), according to any one of claims 1 to 11 as a photocatalyst or as a dopant, in particular in the emitting layers of light-emitting diodes (OLEDs). An electroluminescent device or light emitting diode (OLED) comprising a compound according to any one of claims 1 to 11.

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