EP4182321A1

EP4182321A1 - Organic compounds with delayed fluorescence emission and circularly polarised luminescence and use thereof

Info

Publication number: EP4182321A1
Application number: EP21742816.8A
Authority: EP
Inventors: Grégory PIETERS; Ludovic FAVEREAU; Laurelie POULARD; Max COEHLO; Lucas FREDERIC; Sitthichok KASEMTHAVEECHOK; Jeanne CRASSOUS
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Commissariat a lEnergie Atomique CEA; Institut National des Sciences Appliquees de Rennes; Ecole Nationale Superieure de Chimie de Rennes; Universite Paris Saclay; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Institut National des Sciences Appliquees de Rennes; Ecole Nationale Superieure de Chimie de Rennes; Universite Paris Saclay; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2020-07-16
Filing date: 2021-07-09
Publication date: 2023-05-24
Also published as: FR3112550A1; US20230255105A1; KR20230074110A; WO2022013112A1; FR3112550B1; JP2023533581A

Abstract

The present invention relates to compounds simultaneously having thermally activated delayed fluorescence (TADF), circularly polarised luminescence (CPL) and aggregation-induced emission enhancement (AIEE) properties. The invention also relates to the use of such compounds as a photocatalyst or as a dopant, in particular in the emitting layers of light-emitting diodes (OLEDs), as well as light-emitting devices or light-emitting diodes (OLEDs) comprising such compounds.

Description

DESCRIPTION

ORGANIC COMPOUNDS WITH DELAYED FLUORESCENCE EMISSION AND CIRCULARLY POLARIZED LIGHT

AND THEIR USE Technical field of the invention

The present invention relates to compounds having both the properties of thermally activated delayed fluorescence (TADF), circularly polarized light emission (CPL) and aggregation fluorescence enhancement (AIEE).

The invention also relates to the use of such compounds as a photocatalyst or as a dopant in particular in the emitting layers of light-emitting diodes (OLEDs), as well as light-emitting devices or light-emitting diodes (OLEDs) comprising such compounds.

Technical background

The search for molecules with delayed fluorescence properties is at the heart of the development of efficient light devices at low energy cost. These molecules, used pure or as dopants of the emitting layers of light-emitting diodes (OLED or Organic Light-Emitting Diode in English) make it possible to manufacture luminous devices having a theoretical internal efficiency of 100% (meaning that all the charges injected in the form of current is returned in the form of light) against only 25% for a conventional fluorophore. Until then, the emitter molecules making it possible to achieve such yields were phosphorescent molecules involving organometallic complexes using rare metals such as iridium or platinum. For reasons of both manufacturing cost and sustainability, thermally activated delayed fluorescence molecules (TADF or Thermally Activated Delayed Fluorescence), which can be purely organic, therefore represent a target of choice for researchers in an area in full economic expansion through their applications for low-power lighting and high-resolution display devices.

In addition, the discovery of organic molecules making it possible to emit circularly polarized light (CPL or Circularly Polarized Luminescence in English) is also a field in strong expansion in recent years. In this field, it is complexes involving lanthanides which make it possible to obtain the best performance in terms of the degree of polarization of the light. However, a lot of research work is currently being carried out in order to develop purely organic CPL-emitting molecules to limit manufacturing costs and facilitate their incorporation into devices. Indeed, these small chiral molecules have a strong application potential since they can be used in the design of advanced technology devices allowing, for example, the optical storage of information, the 3D display or the securing of a document.

Furthermore, in the field of application of OLEDs relating to display, molecules exhibiting both properties of delayed fluorescence and of emission of circularly polarized light are particularly attractive. In fact, this type of transmitter makes it possible to limit the loss of brightness of the screens caused by the filters used to reduce the reflection of external light. These optical filters are most often composed of a delay plate (quarter-wave plate) and a polarizer capable of selecting the polarization of the light passing through them and of canceling the reflection on the OLED of the light component. exterior. However, a non-negligible part of the light intensity produced by the molecule in the emitting layer of the OLED is lost for a molecule that does not emit circularly polarized light.

Molecules emitting circularly polarized light are characterized by their quantum efficiency Φ _F (the measure of photon emission efficiency) but also by the asymmetry factor |g _lum | accounting for the amplitude of the circular polarization. This value of g _lum is between -2 and 2, the value 0 represents an absence of circular polarization. For a purely organic fluorophore, the value of |g _lum | is typically between 10 ^-4 and 10 - ³ . For the moment very few organic molecules have high values of both Φ _F (greater than 50% and ideally close to 100%) and |g _lum | (ideally greater than or equal to 10 ^-3 ). In the context of the present invention, the quantum efficiency is defined as follows:

[Chem 1]

In general, the aggregation of fluorophores leads to a strong decrease in the quantum yield via the ACQ phenomenon or Aggregation-Caused Quenching in English. However, for certain fluorophores, an AIEE (Aggregation-Induced Emission Enhancement) phenomenon can be observed where the aggregation will exacerbate the fluorescence of the compounds, thus making it possible to use them at high concentration or in pure solid form.

Furthermore, the combination of the properties of TADF and AIEE makes it possible to envisage the use of emitting layers composed solely of the light-emitting molecule within an OLED device where, in general, the emitter is placed in a matrix in order to to avoid problems of decrease or “quenching” of fluorescence due to aggregation.

It is known that delayed fluorescence emission (TADF) is possible if the energy difference between the lowest energy singlet and triplet excited states (ΔE _ST ) of the fluorescent molecule is small (less than 500 meV). The value of the ΔE _ST is proportional to the overlap integral between the frontier orbitals (OF in the remainder of the presentation) HOMO and LUMO (for Highest and Lowest Unoccupied Occupied 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 structure most commonly used is based on the use of a molecule of the donor-acceptor (DA) type where the dihedral angle between these two entities is as close as possible to 90°. This makes it possible to limit the overlapping of the OFs, the HOMO being mainly located on the electron donor and the LUMO on the acceptor.

G. Pieters et al. (J. Am. Chem. Soc. 2016, 138, 3990-3993) proposed the molecule represented in [Fig. l] in which a chiral unit is attached to an active TADF chromophore. The chiral unit makes it possible to induce chiroptical properties (CPL). The active chromophore here consists of a TADF donor-acceptor system linked to a BINOL-type chiral unit. This design has been widely exemplified by other teams with the use of other donor, acceptor or chiral motifs.

Planar chirality has also been used for the synthesis of CPTADF molecules (molecules combining CPL and TADF properties). Today there are only two examples based on derivatives of [2.2]paracyclophanes published by Zhang et al. (Org. Lett. 2018, 20, 6868) and Zysman-Colman et al. {Chem. Science. 2019, 10, 6689), both in 2019. The first uses the paracyclophane unit both as a source of chirality but also to ensure the separation between OFs: the HOMO is located on the ring carrying the amine, whereas the LUMO is positioned at the level of the boron as shown in [Fig.2]. The second uses the chirality of paracyclophane as a donor group, the HOMO-LUMO separation taking place thanks to a phenyl group acting as a spacer placed between the donor and the acceptor as shown in [Fig.3]. In this example, an intrinsically chiral donor is used to generate CPL.

The need for new molecules which are both emitters via delayed fluorescence, emitting circularly polarized light and possessing AIEE properties still remains. There is therefore a real need for molecules, in particular organic molecules

- thermally activated delayed fluorescence emitters (TADF),

- emitters of circularly polarized light (CPL) characterized by high values both of quantum efficiency Φ _F greater than or equal to 50% in the solid state, and ideally close to 100%, and of asymmetry factor accounting for the amplitude of the circular polarization |g _lum | (greater than or equal to 10 ^-3 in solution), and - possessing AIEE properties (Aggregation-Induced Emission

Enhancement in English) where the aggregation of said molecules will exacerbate their fluorescence thus allowing them to be used at high concentration or in pure solid form, and

- which are durable with a manufacturing cost lower than the cost for known molecules.

Summary of the invention

The present invention relates to a compound of formula (I): in which - X and X' , identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and - Y and Y' , identical or different, represent CR _y , CR _y' , a heteroatom chosen from the group formed by N, O, with R _y and R _y' identical or different, representing a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon, a hydroxyl group, a alkoxy group, an aryloxy group, an amine group of formula NR ₁₄ R ₁₅ with R ₁₄ and R ₁₅ , which are identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or a aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _{z '} , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, a alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR _{1 7} R _{1 8} with R _{1 7} and R ₁₈ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

- R _z and R _{z '} , together with the carbon atoms to which they are linked, form an aryl or a heterocycle chosen from the group formed by:

with R ₁₀ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydoxyl group, an alkoxy group, an aryloxy group, an amine of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted; - R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom , a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

- R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₄₀ R ₄₁ with R ₄₀ and R ₄₁ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 atoms carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and

- R ₃ and R ₄ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by:

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by: with R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , 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, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, an deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; or - R ₁ and R ₂ , on the one hand, and R ₇ and R ₈ , on the other hand, together with the carbon atoms to which they are linked, each form a naphthyl to lead to a fragment of the following formula: with - R ₃ , R ₄ , R ₈ and R _{6 which are} identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 atoms carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; or - R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by:

, and - R ₅ and R ₆ , together with the carbon atoms to which they are bonded, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by:

with R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , 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, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; excluding the following compounds

The chemical structure of the compound of formula (I) extends to all possible function position isomers which can be obtained by moving a functional group to the different carbons of the carbon chain, and to all possible configuration isomers which can be obtained by varying the configuration of the individual chiral centers, axes or surfaces of the compound of formula (I).

The invention also relates to the use of a compound of formula of formula (I), as a photocatalyst or as a doping agent in particular in the emitting layers of light-emitting diodes

(OLEDs).

It further relates to a light-emitting device or a light-emitting diode (OLED) comprising a compound of formula (I). Brief description of figures

Other characteristics and advantages of the invention will appear during the reading of the detailed description which will follow for the understanding of which reference will be made to the appended drawings in which: [FIG. 1] represents a molecule according to G. Pieters et al. (J. Am. Chem. Soc. 2016, 138, 3990-3993) in which a chiral unit is attached to an active chromophore TADF. The active chromophore is constituted here a TADF donor-acceptor system linked to a BINOL-type chiral unit which makes it possible to induce chiroptical properties (CPL).

[Fig. 2] represents a CPL and TADF molecule described by Zhang et al. (Org. Lett. 2018, 20, 6868) using the paracyclophane unit both as a source of chirality but also to ensure the separation between the OFs: the HOMO is located on the ring carrying the amine, while the LUMO is positioned at the level of boron.

[Fig. 3] represents a CPL and TADF molecule described by Zysman-Colman et al. (Chem. Sci. 2019, 10, 6689) using the chirality of paracyclophane as a donor group, the HOMO-LUMO separation taking place thanks to a phenyl group acting as a spacer placed between the donor and the acceptor.

[Fig. 4] represents the different possible ways of de-excitation of the excited state S I after absorption of a photon. The different phenomena present after excitation with their respective lifetime are represented.

The three radiative de-excitation processes presented,

- the prompt fluorescence, i.e. the radiative de-excitation resulting from the relaxation from the excited singlet state of lower energy,

- phosphorescence, and

- delayed fluorescence, i.e. radiative de-excitation resulting from relaxation from the lower-energy excited singlet state preceded by intersystem (and reverse intersystem) crossing between the lower-energy singlet and triplet states, are manifestations of luminescence. When the excitation is light, it is photoluminescence.

[Fig.5] represents Fluorescence decay (after argon degassing) of B2-CNPyrF ₂ . Quantum yields were measured in toluene.

Decline spectrum: the abscissa represents the time in ns, the ordinate represents the fluorescence intensity in counts per second. The quantum yield, which measures the efficiency of photon emission, is calculated relative to a suitable reference whose absorbance and fluorescence spectra overlap with those of the compound studied. The formula used is as follows: where S represents the area under the emission curve of the compound to be studied and S _ref the area under the emission curve of the reference, A and A _ref the absorbances of the compound to be studied and of the reference respectively, n and n _ref are the refractive indices of the media in which the molecule of interest and the reference are found. Finally Φ _ref is the quantum efficiency of the reference.

[Fig. 6] represents the fluorescence decline of B1-TPNF ₂ (under Air (O ₂ ) and after degassing with argon). The abscissa corresponds to the time expressed in μs, and the ordinate corresponds to the fluorescence intensity expressed in counts per second. Quantum yields were measured in toluene. The quantum yield is calculated as indicated above.

Detailed description of the invention

The present invention aims to meet the needs identified above by providing a compound of formula (I): in which

- X and X', identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- Y and Y', identical or different, represent CR _y , CR _y' , a heteroatom chosen from the group formed by N, O, with R _y and R _y' identical or different, representing a hydrogen atom, a deuterium , a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms , a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₄ R _{1 5} with R ₁₄ and R _{1 5} , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 with 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _{z '} , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, a alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₇ R ₁₈ with R ₁₇ and R _{1 8} , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

with R ₁₀ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; - R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom , a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; or - R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms , a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₄₀ R ₄₁ with R ₄₀ and R ₄₁ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and - R ₃ and R ₄ , together with the carbon atoms to which they are attached, form a cyclic alkyl, a aryl or a heterocycle chosen from the group formed by:

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by: with R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R _59, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 with 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, a deuterium, a radical alkyl having 1 to 12 carbon atoms or an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

- R ₁ and R ₂ , on the one hand, and R ₇ and R ₈ , on the other hand, together with the carbon atoms to which they are linked, each form a naphthyl to lead to a fragment of the following formula:

- R ₃ , R ₄ , R ₈ and R _6, identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 atoms of carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where - R ₃ and R ₄ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by:

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by:

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

The compounds of formula (I) according to the invention have the advantage of being both emitters via delayed fluorescence (TADF), able to emit circularly polarized light (CPL) and possessing AIEE properties.

The inventors have found, quite unexpectedly, that the use of a rigid 8-membered heterocycle around which are arranged a polycyclic electron donor unit and a mono- or poly-cyclic electron acceptor unit, allows to generate emitting molecules by delayed fluorescence. The donor units are thus separated from the electron acceptor units by the 8-membered heterocycle. The polycyclic nature of the electron donor can allow the use of chiral molecular fragments (atropoisomerism) and, therefore, make it possible to combine properties of TADF (induced by the constrained geometry of the cycle at 8 which limits the overlap between the orbitals borders (OF in the rest of the presentation) and CPL (generated by the chirality of the electron donor). A wide variety of compounds involving various electron donors and acceptors can thus be synthesized. the present invention, the term "electron donor" refers to any unit, system, reagent, molecule, compound, group etc. comprising a substituent or a functional group having a mesomeric or inductive donor effect, which includes all heterocycles excess electrons The term "electron acceptor" refers to any unit, system, reactant, molecule, compound, group, etc. comprising a substituent or a functional group possessing a negative effect. someric or inductive attractor, which includes all electron-deficient heterocycles. The term “alkyl”, within the meaning of the present invention, 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. As saturated, linear or branched alkyl, mention may be made, for example, of the methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl radicals and their branched isomers. The term "cyclic alkyl", within the meaning of the present invention, a cyclic carbon radical, saturated, optionally substituted, comprising 3 to 12 carbon atoms, for example 3 to 10 carbon atoms, for example 3 to 8 carbon atoms . By way of cyclic alkyl, mention may be made of the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl and adamantyl radicals. The term “aryl” designates a mono- or poly-cyclic aromatic substituent comprising from 6 to 20 carbon atoms. The aryl group can include, for example, 6 to 10 carbon atoms. By way of indication, mention may be made of 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.

The term "heterocycle" or "heterocyclic" denotes a mono- or poly-cyclic substituent, comprising 5 to 10 members, saturated or unsaturated, containing 1 to 3 identical or different heteroatoms, chosen from nitrogen, oxygen, or sulfur. By way of indication, mention may be made of the substituents morpholinyl, piperidinyl, piperazinyl, pyrrolyl, pyrrolidinyl, pyridinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, pyrazinyl, tetrahydrofuranyl, tetrahydropyranyl, thianyl, oxazolinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolidinyl, isothiazolidinyl, , xanthenyl, carbazolyl, furazanyl, phenothiazinyl, phenazinyl, phenoxazinyl, quinolinyl, quinoxalinyl.

The alkyl and aryl radicals and the heterocycles can be optionally substituted by one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl (-CO-alkyl) groups; one or more alkyl radicals; one or more aryl radicals; with alkyl, and aryl as defined in the context of the present invention.

It should be noted that in all substituents, radicals, groups and groups, etc. cited and / or defined in the context of the present invention, one or more hydrogen atoms bit (s) may be optionally substituted (s) with one or more deuterium ^(2H). Representation as used herein in relation to a group, a substituent or chemical moiety, is intended to represent the covalent bond by which said chemical group or moiety is covalently bonded to another chemical group or moiety.

According to a first embodiment, in the compound of formula (I)

- X, X′, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined above; and

- Y and Y', identical or different, represent CR _y , CR _y' with R _y and R _y' , identical or different, representing a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen chosen from the group formed by F, Cl, Br and I, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _{z '} , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, a alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted. The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In a variant of this embodiment, Y and Y' represent CR _y , CR _y' with R _y and R _y' representing a nitrile group (-CN), and R _z and R _z' , identical or different, represent a halogen atom chosen from the group formed by F and Cl. In another variant of this embodiment, Y and Y' represent CR _y , CR _y' with R _y and R _y ', identical or different, representing an atom halogen chosen from the group formed by F and Cl, and R _z and R _{z '} , represent a nitrile group (-CN).

In another variant of this embodiment, Y and Y' represent CR _y , CR _y' with R _y and R _y' , identical or different, representing a hydrogen atom, a deuterium, an aryl radical comprising from 6 to 20 carbon atoms, said aryl radical being optionally substituted as indicated above, and R _z and R _z′ , represent a nitrile group (-CN). By way of example of this first embodiment, the following fragments can be cited:

According to a second embodiment, in the compound of formula (I) - X, X', R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined below. -above ; and - Y and Y', identical or different, represent CR _y , CR _y' a heteroatom chosen from the group formed by N, O, with R _y and R _y' identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _{z '} together with the carbon atoms to which they are bonded, form an aryl or a heterocycle chosen from the group formed by:

with R ₁₀ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted.

In a variant of this embodiment, R ₁₀ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , which are identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, a group alkoxy, an aryloxy group, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, the said alkyl and aryl radicals being optionally substituted. The alkyl radical can be, for example, a methyl, ethyl, propyl, butyl, pentyl, hexyl radical, and their branched isomers.

The aryl radical can be, for example, a phenyl, benzyl, naphthyl or phenanthrenyl radical.

The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In a variant of this embodiment,

- Y and Y', identical or different, represent CR _y , CR _y' a heteroatom chosen from the group formed by N and O, with R _y and R _y' identical or different, being a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _z' together with the carbon atoms to which they are bonded, form:

with R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , which are 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, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 atoms carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above. In another variant of this embodiment,

- Y and Y', identical or different, represent a heteroatom chosen from the group formed by N and O, CR _y , C(R _y ) with R _y and R _y' identical or different, being a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a group amine of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted; and

- R _z and R _z' together with the carbon atoms to which they are bonded, form a heterocycle chosen from the group formed by: with R ₁₀ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above. For example, R ₁₀ represents a hydrogen atom, a deuterium, or a methyl, ethyl, propyl, butyl radical, and their branched isomers, or a phenyl, benzyl or naphthyl radical.

In this other variant, for example, Y and Y', identical or different, represent CR _y , C(R _y ) with R _y and R _y' identical or different, being a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms or an aryl radical comprising from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

In a preferred mode of this other variant, R _z and R _z' together with the carbon atoms to which they are bonded, form with R ₁₀ as defined above. Preferably, R ₁₀ is a phenyl.

By way of example of this second embodiment, the following fragments can be mentioned:

with R ₁₀ as defined below in the context of this second embodiment and these variants.

According to a third embodiment, in the compound of formula (I) - X, X', R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined below. -above ; and

- Y and Y', identical or different, represent a heteroatom chosen from the group formed by N and O, CR _y , CR _y with R _y and R _y' identical or different, representing a hydrogen atom, a deuterium, a nitrile group (-CN); and

- R _z and R _{z '} , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl.

In a variant of this third embodiment, Y represents C- R _y with R _y being a nitrile group (-CN), Y' represents N, and R _z and R _z' , identical or different, represent an atom of halogen selected from the group formed by F and Cl.

By way of example of this third embodiment, the following fragment can be cited:

According to a fourth embodiment, in the compound of formula

(I) - X, X′, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined above; and

- Y and Y', identical or different, represent a heteroatom chosen from the group formed by N and O; and - R _z and R _z' together with the carbon atoms to which they are bonded, form: with R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ , which are 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, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , which are identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 atoms carbon, said alkyl and aryl radicals being optionally substituted.

The alkyl radical can be, for example, a methyl, ethyl, propyl, butyl, pentyl, hexyl radical, and their branched isomers.

The aryl radical can be, for example, a phenyl, benzyl, naphthyl or phenanthrenyl radical. The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In a variant of this fourth embodiment, Y and Y' represent N and R _z and R _z' together with the carbon atoms to which they are linked, form: with R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , which are 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, said alkyl and aryl radicals being optionally substituted.

The aryl radical can be, for example, a phenyl, benzyl or naphthyl radical.

As an example of this fourth embodiment, the following fragment can be cited:

According to a fifth embodiment, in the compound of formula (I)

- X, X', Y, Y', R _z and R _z' are as defined above; and

- R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom , a deuterium, a radical alkyl having 1 to 12 carbon atoms or an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In a variant of this fifth embodiment,

- X and X' represent O; and

- Y, Y', R _z and R _z' are as defined above; and

- R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical comprising 1 to

12 carbon atoms, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above.

In this variant, the alkyl radical is, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.

By way of example of this fifth embodiment, the following fragments may be cited:

According to a sixth embodiment, in the compound of formula (I)

- X and X', identical or different, represent a heteroatom chosen from the group formed by O, and N- R ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- Y, Y', R _z and R _z' are as defined above; and

- R ₃ and R ₄ , together with the carbon atoms to which they are linked, form a cyclic alkyl or an aryl chosen from the group formed by: and

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl or an aryl chosen from the group formed by: with

- R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₅₆ , R ₅₇ , R ₅₈ , and R ₅₉ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , which are identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In a variant of this sixth embodiment, - X and X', identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above;

- Y, Y', R _z and R _z' are as defined above;

- R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted, and

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form a cyclic alkyl or an aryl chosen from the group formed by:

, and

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl or an aryl chosen from the group formed by: with R ₄₂ , R ₄₃ , R ₄₄ , and R ₄₅ , 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 , said alkyl and aryl radicals being optionally substituted as indicated above.

In another variant of this sixth embodiment, - X and X', identical or different, represent a heteroatom chosen from the group formed by O and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- Y, Y', R _z and R _z' are as defined above; and

- R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above, and

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form: - R ₅ and R ₆ , together with the carbon atoms to which they are bonded, form: with

- R ₁₁ , R ₅₆ , R ₅₇ , R ₅₈ , and R _59, 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, said alkyl and aryl radicals being optionally substituted. In the variants of this embodiment, the alkyl radical can be, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.

By way of example of this sixth embodiment, the following fragments may be cited: with R ₁ , R ₂ , R ₇ , R ₈ , R ₁₁ , R ₅₆ , R ₅₇ , R ₅₈ , and R ₅₉ , as defined above. Preferably, R ₁ , R ₂ , R ₇ , R ₈ , R ₁₁ , R ₅₆ , R ₅₇ , R ₅₈ , and R ₅₉ , which are identical or different, represent a hydrogen atom, a deuterium, a chosen alkyl radical, for example, from the group formed by a methyl, ethyl, propyl, butyl radical, and their branched isomers, an aryl radical chosen, for example, from the group formed by a phenyl, benzyl, naphthyl and phenanthrenyl radical.

According to a seventh embodiment, in the compound of formula (I)

- X and X', identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or a radical aryl containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- Y, Y', R _z and R _z' are as defined above; and

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form an aryl or a heterocycle chosen from the group formed by:

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by: with

- R ₁₁ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , 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, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, the said alkyl radicals and aryl being optionally substituted. The substituents of the alkyl and aryl radicals can be, for example, one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more carbonyl group (-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. Preferably, the substituents of the alkyl and aryl radicals are one or more nitro (-NO ₂ ) groups; one or more nitrile groups (-CN); one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more carbonyl group (-CO-alkyl). In this variant, the alkyl radical can be, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.

In a variant of this seventh embodiment,

- X and X', identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or a radical aryl containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above; and

- Y, Y', R _z and R _z' are as defined above; and

- R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above; and

- R ₃ , R ₄ , R ₈ and R ₆ are as defined above; and

- R ₁₁ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, a aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted as indicated above.

By way of example of this seventh embodiment, the following fragments may be cited:

with R ₁ , R ₂ , R ₇ , R ₈ , R ₁₁ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , as defined above.

Preferably, R ₁ , R ₂ , R ₇ , R ₈ , R ₁₁ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , which are identical or different, represent a hydrogen atom, a deuterium, an alkyl radical chosen, for example, from the group formed by a methyl, ethyl, propyl, butyl radical, and their branched isomers, an aryl radical chosen, for example, from the group formed by a phenyl, benzyl, naphthyl and phenanthrenyl radical.

According to an eighth embodiment, the compound of formula (I) is chosen from the group formed by: The compounds of formula (I) of the invention can be prepared by a process comprising the following steps:

1. The donor (1 to 10 mmol) and acceptor (1 to 10 mM) reagents are placed in a flask containing a base chosen from among Na ₂ CO ₃ , K ₂ CO ₃ or Cs ₂ CO ₃ , NaH, and a suitable organic solvent such as, for example, a solvent chosen from N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), or dimethylacetamide (DMA) under a nitrogen or argon atmosphere.

2. The reaction mixture is stirred at room temperature (20+5°C) for 8 to 12 hours.

3. The reaction is stopped by adding distilled water and an organic solvent chosen, for example, from dichloromethane (CH ₂ CI ₂ ), ethyl acetate (EtOAc), or monochloromethane (CH ₃ CI ). The mixture is then extracted with an organic solvent such as, for example, a solvent chosen from dichloromethane (CH ₂ CI ₂ , ethyl acetate (EtOAc), or monochloromethane (CH ₃ CI). The combined organic phases are dried for example over MgSO ₄ , filtered and concentrated under reduced pressure to give the compound of formula

(I).

Purification can be carried out by any purification technique known to those skilled in the art. Flash chromatography on silica gel using, for example, a mixture of solvents, the solvents being chosen, for example, from cyclohexane, petroleum ether, hexane, ethyl acetate, DCM, CH ₃ Cl, toluene) as eluent. An example of eluent is a cyclohexane/dichloromethane (1/1) mixture.

The aforementioned solvents have been used, by way of example, and are in no way limiting.

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

A subject of the invention is therefore the use of a compound of formula (I) according to the invention as a photocatalyst, in particular in reactions for the activation of CH bonds, reactions for the formation of CC and CX bonds with X being a heteroatom, or as a dopant in particular in the emitting layers of organic light-emitting diodes (OLEDs).

A further subject of the invention is a light-emitting device or a light-emitting diode comprising a compound of formula (I) according to the invention. EXAMPLES

The various reagents and solvents used in the process of the invention and in the examples are, in general, commercial compounds or can be prepared by any process known to those skilled in the art.

The compounds synthesized were characterized by ¹ H NMR, ¹³ C NMR and ¹⁹ F NMR analysis techniques on a Bruker Avance 400 MHz spectrometer. The chemical shifts are reported in parts per million (ppm) parameterized on the residual peaks of the deuterated solvent used and the coupling constants are indicated in Hertz (Hz). The multiplicity of peaks is denoted by singlet (s), doublet (d), triplet (t). Multiplicities that cannot be interpreted are reported as multiplets (m).

The synthesized compounds were characterized by the techniques of analysis and mass spectrometry using the ESI-Quadripole autopurify instrument, Waters (pump: 2545, mass: ZQ2000) and mass spectrometry.

UV-visible spectra were recorded on a Cary 50 or Cary 400 (Agilent) dual beam spectrometer using a 10 mm path quartz cell. Circular dichroism (CD) spectra were recorded on a Jasco spectropolarimeter (model J-815) equipped with a thermostatically controlled Peltier cell holder and an Xe laser. Data was recorded at 20°C using a 1mm*1cm cell. The signals obtained were processed by subtracting the contribution of the solvent and the cells.

The emission spectra were measured on a Fluoromax-3 (Horiba) or Fluoromax-4 (Horiba) or Fluorolog (Horiba) spectrofluorimeter. A right angle configuration was used. The optical density of the samples was checked to be less than 0.1 to avoid reabsorption artifacts.

Fluorescence decay curves in the ns regime were obtained by the time-correlated single-photon counting method (TCSPC) with a femtosecond laser excitation composed of a Titanium Sapphire laser (Tsunami, Spectra-Physics) pumped by a lined Nd:YV04 laser (Millennia Xs, Spectra-Physics). The 990 nm light pulses from the oscillator were picked by an acousto-optic crystal at a repetition rate of 4 MHz, then tripled to 330 nm by nonlinear crystals. Fluorescence photons were detected at 90° through a monochromator and a magic angle polarizer by means of a photomultiplier

Hamamatsu MCP R3 809U, connected to a TCSPC SPC-630 module from Becker & Hickl. The instrumental response function was recorded before each decay measurement with an fwhm (full-width at half-maximum) of ~25 ps. Fluorescence data were analyzed using the Globals software package developed at the Laboratory for Fluorescence Dynamics at the University of Illinois at Urbana-Champaign, which includes reconvolution analysis and a nonlinear least-squares global minimization method. . The ps fluorescence decay curves were obtained using an Edinburgh LP920 laser flash photolysis spectrometer combined with a tripled Nd:YAG (Continuum) laser at 355 nm via nonlinear crystals. This third harmonic is optimized to pump an OPO which can generate a 425nm signal. Fluorescence photons were detected at 90° through a high-pass filter and monochromator using a Hamamatsu R928 photomultiplier. The Levenberg-Marquardt algorithm was used for nonlinear least-squares fitting (tail fitting) as implemented in the L900 software (Edinburgh instrument). In order to estimate the goodness of fit, the weighted residuals were calculated.

Circularly Polarized Luminescence or CPL measurements (general):

A molecule can preferentially absorb circularly polarized light, similarly it can also emit excess circularly polarized light by radiative decay as 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 speak of then from CPL, or else 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 with circular dichroism, to measure CPL one measures the difference in intensity (Δ/(λ)) between the left circularly polarized light emission (/ _L /(λ)) versus the circularly polarized light emission right-hand polarized (/ _R /(λ)): Δ/(λ) = / _L (λ) - / _R (λ)

The measurements of Δl(λ) are quite complex since they can be subject to many experimental artifacts (linearly polarized light, birefringence phenomena) and to a problem related to the detection limit. In fact, in general, the proportion of circularly polarized light is very low compared to the total light emitted I(λ), therefore the photomultipliers used must be very efficient.

In order to be able to compare the emission of circularly polarized light between fluorophores, the luminescence asymmetry factor should be used: where I(λ) represents the total luminescence intensity. Due to the "factor 2", the g _lum can take on values between −2 and 2, similar to the g _abs , representing total emission of right or left circularly polarized light. In the same way as for the CD, if the value of g _lum is null, 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 the 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 happens that the molecule changes geometry with respect to its ground state. This is why it is possible to have a g _abs different from 0 and a _{zero g lum} (and theoretically the converse is also possible, but has never been observed). A loss of chiral information can occur if the geometry of the molecule is changed, and if the radiative decay transition does not involve the intrinsically chiral parts of the molecule.

It is also possible to determine theoretically, i.e. by modeling and calculations, the values of g _lum via the following formula: In this formula m and m represent respectively the electric and magnetic dipole transition moments in the excited state, θ is the angle between these two vectors.

With this formula, it is easy to understand that the larger the values of the vector norms, the higher the value of g _lum will be (if . Notwithstanding, in practice m is often very small compared to m

(hence the approximation, thus the g _lum is directly proportional to |m| and inversely proportional to |μ|. Therefore, high values of g _lum 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 perform specific transitions (Laporte f — f transition, theoretically prohibited, but observable thanks to spin-orbit coupling) which give a very high magnetic transition moment and a weak electrical transition moment. This is why, despite the high values of g _lum obtained (the maximum value measured so far is 1.38), the quantum yields of this type of complex are low (around a few percent in the best case).

Delayed fluorescence

Reverse Intersystem Crossover (rISC)

As mentioned previously, from state T ₁ it is possible for a molecule to return to an excited singlet state S ₁ . 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 S ₁ and the lowest energy triplet state T ₁ (ΔE _ST ) is small enough, one speaks of inverse intersystem crossing (called rISC for reverse InterSystem Crossing), we then have the following transition: T ₁ → S ₁ .

Like the intersystem crossing, the inverse intersystem crossing can only take place if the initial state (T ₁ ) has a lifetime long enough and the speed of the reverse intersystem crossing is high enough.

This phenomenon is energetically dependent since one passes from a low energy state (T ₁ ) to a higher energy state (S ₁ ). Thus, it is considered that for there to be spontaneously, at ambient temperature (20 s 5°C), inverse intersystem crossing, the energy difference between S ₁ and T ₁ must be less than 100 meV: ΔE _ST ≤ 100 meV. This value is often debated because it depends on the fluorophore studied: some molecules with a ΔE _ST greater than 100 meV can still exhibit delayed fluorescence properties. The limit value of 360 meV is also found in the literature.

The ΔE _ST 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 ΔE _ST . The challenge of a molecular design to have a significant intersystem crossing lies in obtaining a good spatial separation of these boundary orbitals. Various molecular designs have been developed to fulfill these conditions, the most commonly used involving fluorophores of the donor-acceptor type, where these two units form a dihedral angle as close as possible to 90°. This makes it possible to position the HOMO mainly on the donor group and the LUMO mainly on the acceptor. However, care must be taken not to completely separate the two frontier orbitals because the quantum efficiency 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 ΔE _ST and to preserve interesting quantum yields.

Thermally Activated Delayed Fluorescence

After crossing inverse intersystem the molecule returns to state S _1. Therefore it is possible for it to emit fluorescence

(de-excitation S ₁ →S ₀ ) which will have the same emission wavelength as the prompt fluorescence. However, as the molecule has gone through several states, the lifetime of this fluorescence is different, it is longer, of the order of 10 ^-8 to 10 ^-5 seconds, which is why this phenomenon is called “delayed fluorescence”.

However, the term “delayed fluorescence” used in French omits an important part of the phenomenon. Indeed in English, delayed fluorescence is called "Thermally Activated Delayed Fluorescence" (abbreviated TADF), which could be translated as: "thermally activated delayed fluorescence". Because of inverse intersystem crossing, which is a temperature-dependent process, the delayed fluorescence is also temperature-dependent. Thus, the more the temperature of the medium increases, the more the intersystem crossing will be favored, and the more the molecules will be able to return to the state S ₁ to emit delayed fluorescence.

Fa [Fig. 4] shows the different phenomena present after excitation with their respective lifetime. All three radiative decay processes shown, namely, prompt fluorescence, phosphorescence and delayed fluorescence, are manifestations of luminescence. When the excitation is light, it is photoluminescence.

Photophysical and TADF data: To demonstrate the TADF properties of the compounds of the invention, it is necessary

- check 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 deactivates the triplet state), and

- see if an increase in quantum efficiency (Φ _F ) is observed between the solution in air and the solution degassed with argon.

Example 1: Synthesis of B2-CNPyrF ₂ Chemical formula: C ₃₄ H ₂₂ F ₂ N _4O2 Molar mass: 556.57 g. mol ^-1

[Table 1]

In a flask containing 3,3',9,9'-tetramethyl-9H,9'Fl-[1,1'-bicarbazole]-2,2'-diol (B2, 0.0310 g, 0.07 mmol ), 2, 3,5,6-tetrafluoro-4-pyridinecarbonitrile (CNPyrF ₄ , 0.0167 g, 0.09 mmol) and K ₂ CO ₃ (0.0376 g, 0.27 mmol), are added DMF (1 mL) under a nitrogen atmosphere. The reaction mixture is stirred at ambient temperature (20+5° C.) for 16 hours. The reaction is stopped by adding distilled water and dichloromethane to the pale yellow suspension formed. The mixture is extracted twice with dichloromethane. The combined organic phases are dried over MgSO ₄ , filtered and concentrated under reduced pressure to give a yellow powder purified by flash chromatography on silica gel using a cyclohexane/dichloromethane mixture (1/1) as eluent. 5,6-difluoro-2,9,15,16-tetramethyl-15,16-dihydropyrido[2',3':2,3]

[1,4]dioxocino[6,5-a:7,8-a']dicarbazole-7-carbonitrile (B2-CNPyrF ₂ ) is obtained as a white solid (0.0470 g, yield (calculated by relative to the starting BICOL B2) = 99%) and characterized by NMR. . The two enantiomers are then separated by chiral chromatography in the supercritical phase. ¹ H NMR (CDCl ₃ , 400MHz): δ (ppm) = 8.10 (m, 2H), 8.06 (dd, J = 7.63 Hz, 0.73 Hz, 2H), 7.48 (m, 2H), 7.29 (m, 4H) , 3.21 (sec, 3H), 3.12 (sec, 3H), 2.62 (sec, 3H), 2.55 (sec, 3H).

¹³ C NMR (CDCl ₃ , 100 MHz): δ (ppm) = 149.19, 148.50, 142.89, 142.79, 126.39, 126.35, 123.09, 123.04, 122.33, 122.15, 122.10, 121.602, 9, 1.602, 9, 1.602, 92.1.

119.93, 112.02, 111.84, 109.19, 109.17, 30.66, 30.59, 17.91, 17.26 Quantum yields measured in toluene: Φ _F (O ₂ ) = 5% (fluo prompt); Φ _F (Ar) = 11% (prompt fluo + delayed fluo). "Prompt Fluo" means the prompt fluorescence, that is to say the fluorescence with a short lifetime, of the order of about ten ns, corresponding to the radiative de-excitation of the state S ₁ towards the state ground without passing through the triplet state;

"Delayed Fluo" means delayed fluorescence, i.e., radiative decay arising from relaxation from the lower energy excited singlet state preceded by intersystem (and inverse intersystem) crossover between the singlet and triplet states of lower energy.

The apparatus and the method used to measure these parameters have already been specified.

To determine the quantum yield, the fluorescence signal of the product obtained is compared with that of a reference of _{known Φ F} emitting in a close wavelength range. In the present case, said reference of _{known Φ F} is coumarin 102. The g _lum for this compound is 0.8×10 ^-3 (toluene, C=10 ^-5 ).

Example 2 Synthesis of B ₂ -TPNF ₂ Chemical formula: C ₃₆ H ₂₂ F ₂ N ₄ O ₂ Molar mass: 580.59 g. mol ^-1

[Table 2]

In a flask containing BicolB (0.0500 g, 0.12 mmol), tetrafluoroterephthalonitrile (0.0287 g, 0.14 mmol) and K ₂ CO ₃ (0.0551 g, 0.40 mmol) is added DMF (1.5 ml) under a nitrogen atmosphere. The reaction mixture is stirred at ambient temperature (20±5° C.) for 12 hours. The reaction is stopped by adding distilled water and dichloromethane to the pale yellow suspension formed. The mixture is extracted twice with dichloromethane. The combined organic phases are dried over MgSO ₄ , filtered and concentrated under reduced pressure to give a yellow powder purified by flash chromatography on silica gel using a cyclohexane/dichloromethane mixture (1/1) as eluent.

Compound B ₂ -TPNF ₂ is obtained in the form of a yellow solid (0.0455 g, yield (calculated relative to the starting BICOL B2) =

65%). The two enantiomers are then separated by chiral chromatography in the supercritical phase.

¹ H NMR (CDCl ₃ , 400MHz): δ (ppm) =8.03 (d, 7.50 Hz, 2H), 8.00 (s, 2H), 7.41 (dd, 11.45 Hz, 3.97 Hz, 2H), 7.23 (d, 4H ), 7.17, 3.12 (s, 6H), 2.52 (s, 6H) ¹³ C NMR (CDCl ₃ , 100 MHz): δ (ppm) =149.49, 142.91, 138.10, 126.54, 123.35, 122.44, 122.03, 121.236, 120.236, 120.236 , 120.06, 111.90, 109.24, 29.86, 18.04 Quantum yields measured in toluene: Φ _F (O ₂ ) = 10% (fluo prompt); Φ _F (Ar) = 26% (prompt fluo + delayed fluo).

The g _lum measured for this compound is ^{1.8×10 -3} (toluene, C=10 ^-5 ). Example 3 Synthesis of B1-TPNF ₂ Chemical formula: C ₃₄ H ₁₈ F ₂ N ₄ O ₂ Molar mass: 552.54 g. mol ^-1

[Table 3] In a flask containing 9,9'-tetramethyl-9H,9'H-[4,4'-bicarbazole]-3,3'-diol (B1, 0.040 g, 0.13 mmol), tetrafluoroterephthalonitrile (TPNF4, 0.022 g, 0.13 mmol) and K ₂ CO ₃ (0.070 g, 0.63 mmol), DMF (5 mL) is added under an argon atmosphere. The reaction mixture is stirred at ambient temperature (20+5° C.) for 16 hours. The reaction is stopped by adding distilled water and ethyl acetate to the pale yellow suspension formed. The mixture is extracted twice with ethyl acetate. The combined organic phases are dried over MgSO ₄ , filtered and concentrated under reduced pressure to give a yellow powder purified by chromatography on silica gel using a cyclohexane/ethyl acetate mixture (1/1) as eluent.

5,6-difluoro-2,9,15,16-tetramethyl-15,16-dihydropyrido[2',3':2,3]

[1, 4] dioxocino [6,5-a: 7,8-a '] dicarbazole-7-carbonitrile (B1-TPNF ₂₎ is obtained in the form of a white solid (0.0430 g, yield (calculated relative to the starting BICOL)=76%) and characterized by NMR. The two enantiomers are then separated by chiral chromatography in the supercritical phase. ¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 7.64 (d, J = 8.8 Hz, 2H), 7.56 (d, J = 8.8 Hz, 2H), 7.45 (d, J = 8.3 Hz , 2H), 7.34 (ddd, J = 8.3, 7.1, 1.2 Hz, 2H), 6.94 (d, J = 8.0 Hz, 2H), 6.64 (ddd, J = 8.0, 7.0, 1.0 Hz, 2H), 3.98 ( s, 6H). ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz): δ (ppm): 148.5, 147.8, 145.3, 145.2, 144.7, 142.2, 139.4, 126.5, 122.8, 122.0, 121.6, 120.9, 118.9, 110.6, 1109.6, 110.6, 110.6, 108.7, 102.8, 29.4. HRMS calculates for [M+Na] ⁺ ( C ₃₄ H ₁₈ N ₄ O ₂ F ₂ Na): 575.129 found 575.1288 (0 ppm) Quantum yields measured in toluene: Φ _F (O ₂ ) = 6% (fluo prompt) ; Φ _F (Ar) = 15% (prompt fluo + delayed fluo). The g _lum measured for this compound is 0.7 x 10 ^-3 (toluene, C = 10 ^-5 ). Example 4: Synthesis of C1-(S)-TPNBINOL-(R) Chemical formula: C60H34N ₄ O2 Molar mass: 842.2682 g.mol ^-1

[Table 4]

In a flask containing N2,N2'-diphenyl-[l,l'-binaphthalene]-2,2'-diamine (C 1(S), 0.060 g, 0.14 mmol) dissolved in DMF (1 mL) , NaH (0.012 g, 0.30 mmol) is added under an argon atmosphere at 0°C. The reaction mixture is stirred at 0° C. for 5 minutes and then the reaction mixture is allowed to return to ambient temperature (approximately 10 min). Subsequently, a solution of the compound TPNBINOLF ₂ (0.061 g, 0.14 mmol) in DMF (1 mL) is slowly added to the reaction mixture. After this addition, the solution is stirred overnight at room temperature. The reaction is stopped by adding distilled water and ethyl acetate. The mixture is extracted twice with ethyl acetate. The combined organic layers are dried over MgSO ₄ , filtered and concentrated under reduced pressure to give a yellow powder purified by chromatography on silica gel using a cyclohexane/ethyl acetate mixture (80/20) as eluent.

The product C 1-(S)-TPNBINOL-(R) is obtained in the form of a yellow solid (0.0740 g, yield (calculated with respect to the starting diamine)=64%) and characterized by NMR.

¹ H NMR (400 MHz, CDCI ₃ ) δ 8.13 (d, J = 8.8 Hz, 2H), 8.01 (d, J = 8.2 Hz, 2H), 7.95 (d, J = 8.5 Hz, 2H), 7.79 (d , J = 8.8 Hz, 2H), 7.75 (d, J = 8.5 Hz, 2H), 7.71 (d, J = 8.3 Hz, 2H), 7.56-7.52 (m, 2H), 7.47 (d, J = 8.0 Hz , 2H), 7.43 - 7.37 (m, 2H), 7.32-7.38 (m, 2H), 7.14 - 7.06 (m, 4H), 6.59 (t, J = 7.4 Hz, 2H), 6.45 (d, J = 8.1 Hz, 2H), 6.31 (t, J = 7.4 Hz, 2H), 6.21 (dd, J = 7.8, 6.8 Hz, 2H), 5.48 (d, J = 8.0 Hz, 2H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 149.7, 148.6, 146.9, 141.4, 139.6, 137.0, 132.8, 132.2, 132.2, 132.0, 131.3, 130.6, 128.4, 128.3, 127.6, 127.7, 127.6, 127.6,

127.4, 127.3, 126.6, 126.3, 126.2, 126.0, 125.9, 125.0, 121.0, 120.7,

118.4, 114.2, 112.8, 112.3.

HRMS calculates for [M+Na] ⁺ (C ₃₄ H ₁₈ N ₄ O ₂ F ₂ Na): 843.2760 found 843.2760 (0 ppm)

Quantum yields measured in toluene: Φ _F (O ₂ )=5% (fluo prompt); Φ _F (Ar) = 9% (prompt fluo + delayed fluo).

The g _lum measured for this compound is ^{1.6×10 -3} (toluene, C=10 ^-5 ).

Example 5: Comparative example

The molecule of formula A1 represented in [Fig.1] and described by G. Pieters et al. (J. Am. Chem. Soc. 2016, 138, 3990-3993) was synthesized according to the procedure described in this publication.

The CPL data of the Al molecule and of the compounds B2-CNPyrF ₂ of example 1 and B2-TPNF ₂ of example 2 were calculated according to the method described above and compared.

Molecule A1: g _lum (λ _max ) = 0.3 x 10 ^-3 B2-CNPyrF ₂ : g _lum (λ _max ) = 0.8 x 10 ^-3 B2-TPNF ₂ : g _lum (λ _max ) = 1 , 8 X 10 ^-3 B l-TPNFl: g _lum (λ _max ) = 0.7 X 10 ^-3 C 1-TPNBinol: g _lum (λ _max ) = ^{1.6 x 10 -3}

In conclusion, compared to the CPTADF molecule (Al molecule) exhibiting AIEE properties, the compounds B2-TPNF ₂ , _{B2-CNPyrF 2} , B1-TPNF ₂ and C 1(S)-TPNBINOL(R) have values of asymmetry factor ( g _lum ) much higher (up to 6 times).

Claims

CLAIMS 1. Compound of formula (I) in which

- Y and Y', identical or different, represent CR _y , CR _y' a heteroatom chosen from the group formed by N, O, with R _y and R _y' identical or different, representing a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₄ R ₁₅ with R ₁₄ and R ₁₅ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 atoms carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R _z and R _{z '} , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F, Cl, Br and I, a alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, a amine group of formula NR ₁₇ R ₁₈ with R ₁₇ and R ₁₈ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 atoms carbon, said alkyl and aryl radicals being optionally substituted; Where

- R _z and R _z' , together with the carbon atoms to which they are bonded, form an aryl or a heterocycle chosen from the group formed by

with R ₁₀ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted;

- R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical comprising from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom , a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

- R ₁ , R ₂ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, a group amine of formula NR ₄₀ R ₄₁ with R ₄₀ and R ₄₁ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms , said alkyl and aryl radicals being optionally substituted, and

with R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , 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, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

with

- R ₃ , R ₄ , R ₅ and R _{6 which are} identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 atoms of carbon or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; Where

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl, an aryl or a heterocycle chosen from the group formed by: with R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ , 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, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , identical or different, representing a hydrogen atom, an deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; excluding the following compounds

2. Compound according to claim 1, characterized in that

- Y and Y' represent CR _y , CR _y' with R _y and R _y' , representing a nitrile group (-CN), and R _z and R _z' , identical or different, represent a halogen atom chosen from the group formed by F and Cl; Where - Y and Y' represent CR _y , CR _y' with R _y and R _y' ' , identical or different, representing a halogen atom chosen from the group formed by F and Cl, and R _z and R _z' , represent a nitrile group (-CN); Where

- Y and Y' represent CR _y , CR _y' with R _y and R _y ', identical or different, representing a hydrogen atom, a deuterium, an aryl radical comprising from 6 to 20 carbon atoms, said aryl radical being optionally substituted, and R _z and R _z' , represent a nitrile group (-CN).

3. Compound according to claim 1, characterized in that

- R _z and R _z' together with the carbon atoms to which they are bonded, form:

with R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R _{3 1} , R ₃₂ , R ₃₃ and R ₃₄ , 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, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

4. Compound according to claim 1, characterized in that - Y and Y′, identical or different, represent a heteroatom chosen from the group formed by N and O, CR _y , C(R _y′ ) with R _y and R _{y '} , identical or different, being a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl, an alkyl radical comprising 1 to 12 atoms of carbon, an aryl radical containing from 6 to 20 carbon atoms, an amine group of formula NR ₃₅ R ₃₆ with R ₃₅ and R ₃₆ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical comprising from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and - R _z and R _z' together with the carbon atoms to which they are bonded, form a heterocycle chosen from the group formed by: with R ₁₀ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

5. Compound according to claim 1, characterized in that

- Y and Y', identical or different, represent a heteroatom chosen from the group formed by N and O, CR _y , CR _y with R _y and R _y' , identical or different, representing a hydrogen atom, a deuterium, a nitrile group (-CN); and - R _z and R _z' , identical or different, represent a hydrogen atom, a deuterium, a nitrile group (-CN), a halogen atom chosen from the group formed by F and Cl.

6. Compound according to claim 1, characterized in that - Y and Y 'represent N and R _z and R _z' together with the carbon atoms to which they are linked, form: with R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , which are 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, said alkyl and aryl radicals being optionally substituted.

7. Compound according to any one of claims 1 to 6, characterized in that - X and X′ represent O; and

- R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ , identical or different, represent a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms, an amine group of formula NR ₁₂ R ₁₃ with R ₁₂ and R ₁₃ , identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 atoms carbon, said alkyl and aryl radicals being optionally substituted.

8. Compound according to any one of claims 1 to 6, characterized in that

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form a cyclic alkyl or an aryl chosen from the group formed by: - R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl or an aryl chosen from the group formed by: with - R ₁₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₅₆ , R ₅₇ , R ₅₈ , and R ₅₉ , which are identical or different, representing a hydrogen atom, a deuterium, an alkyl radical comprising 1 to 12 carbon atoms, an aryl radical containing from 6 to 20 carbon atoms, a hydroxyl group, an alkoxy group, an aryloxy group, an amine group of formula NR ₆₁ R ₆₂ with R ₆₁ and R ₆₂ , which are identical or different, representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.

9. Compound according to any one of claims 1 to 6 and 8, characterized in that

- X and X', identical or different, represent a heteroatom chosen from the group formed by O, and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or a radical aryl containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted;

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form a cyclic alkyl or an aryl chosen from the group formed by: , and

- R ₅ and R ₆ , together with the carbon atoms to which they are linked, form a cyclic alkyl or an aryl chosen from the group formed by: with R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅ , which are 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, said alkyl and aryl radicals being optionally substituted.

10. Compound of formula (I) according to any one of claims 1 to 6 and 8, characterized in that

- X and X', identical or different, represent a heteroatom chosen from the group formed by O and NR ₉ with R ₉ representing a hydrogen atom, a deuterium, an alkyl radical containing 1 to 12 carbon atoms or an aryl radical containing from 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted; and

- R ₃ and R ₄ , together with the carbon atoms to which they are bonded, form:

- R ₅ and R ₆ , together with the carbon atoms to which they are bonded, form: with

- R ₁₁ , R ₅₆ , R ₅₇ , R ₅₈ , and R _59, 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 atoms of carbon, said alkyl and aryl radicals being optionally substituted.

11. Compound of formula (I) according to any one of claims 1 to 10, characterized in that it is chosen from the group formed by:

12. Use of a compound of formula 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).

13. Light-emitting device or light-emitting diode (OLED) comprising a compound according to any one of claims 1 to

11.