EP4182321A1 - Composes organiques a emission de fluorescence retardee et de lumiere circulairement polarisee et leur utilisation - Google Patents
Composes organiques a emission de fluorescence retardee et de lumiere circulairement polarisee et leur utilisationInfo
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- EP4182321A1 EP4182321A1 EP21742816.8A EP21742816A EP4182321A1 EP 4182321 A1 EP4182321 A1 EP 4182321A1 EP 21742816 A EP21742816 A EP 21742816A EP 4182321 A1 EP4182321 A1 EP 4182321A1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
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- C07D245/00—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms
- C07D245/04—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/06—Peri-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/20—Delayed fluorescence emission
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- 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).
- TADF thermally activated delayed fluorescence
- CPL circularly polarized light emission
- AIEE aggregation fluorescence enhancement
- 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.
- OLEDs light-emitting diodes
- 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.
- Molecules emitting circularly polarized light are characterized by their quantum efficiency ⁇ F (the measure of photon emission efficiency) but also by the asymmetry factor
- This value of g lum is between -2 and 2, the value 0 represents an absence of circular polarization.
- is typically between 10 -4 and 10 - 3 .
- very few organic molecules have high values of both ⁇ F (greater than 50% and ideally close to 100%) and
- the quantum efficiency is defined as follows:
- 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.
- TADF delayed fluorescence emission
- 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).
- 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].
- an intrinsically chiral donor is used to generate CPL.
- TADF thermally activated delayed fluorescence emitters
- CPL circularly polarized light
- 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
- R z and R z ' 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;
- 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
- 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
- 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 prompt fluorescence i.e. the radiative de-excitation resulting from the relaxation from the excited singlet state of lower energy
- 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 ⁇ 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 ⁇ s, 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.
- the present invention aims to meet the needs identified above by providing a compound of formula (I): in which
- - X and X' 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 ' 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;
- 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 al
- 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;
- 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 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 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.
- TADF delayed fluorescence
- CPL circularly polarized light
- 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).
- 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.
- 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.
- 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.
- 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 .
- cyclic alkyl 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.
- 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.
- 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.
- 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.
- 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.
- - 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.
- 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).
- 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.
- 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).
- 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).
- -CN nitrile group
- - 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 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 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, pen
- 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.
- 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).
- 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).
- - 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 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.
- 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
- - Y and Y' 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 10 represents 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.
- 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.
- Y and Y' 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.
- R z and R z' together with the carbon atoms to which they are bonded, form with R 10 as defined above.
- R 10 is a phenyl.
- - 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.
- Y represents C- R y with R y being a nitrile group (-CN)
- Y' represents N
- R z and R z' identical or different, represent an atom of halogen selected from the group formed by F and Cl.
- - 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.
- 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).
- 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 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 or naphthyl radical.
- 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.
- 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).
- 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).
- 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
- the alkyl radical is, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.
- the aryl radical can be, for example, a phenyl, benzyl, naphthyl or phenanthrenyl radical.
- - X and X' 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
- 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 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.
- 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).
- - X and X' 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;
- 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 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.
- - X and X' 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 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 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.
- the alkyl radical can be, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.
- the aryl radical can be, for example, a phenyl, benzyl, naphthyl or phenanthrenyl radical.
- R 1 , R 2 , R 7 , R 8 , R 11 , R 56 , R 57 , R 58 , and R 59 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.
- - X and X' 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
- 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 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.
- 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).
- the alkyl radical can be, for example, a methyl, ethyl, propyl, butyl radical, and their branched isomers.
- the aryl radical can be, for example, a phenyl, benzyl, naphthyl or phenanthrenyl radical.
- - X and X' 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
- 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;
- R 3 , R 4 , R 8 and R 6 are as defined above;
- 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.
- 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:
- 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.
- a base chosen from among Na 2 CO 3 , K 2 CO 3 or Cs 2 CO 3 , NaH
- 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.
- DMF N,N-dimethylformamide
- NMP N-methyl-2-pyrrolidone
- DMA dimethylacetamide
- the reaction mixture is stirred at room temperature (20+5°C) for 8 to 12 hours.
- 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 ).
- 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
- 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.
- solvents being chosen, for example, from cyclohexane, petroleum ether, hexane, ethyl acetate, DCM, CH 3 Cl, toluene
- eluent is a cyclohexane/dichloromethane (1/1) mixture.
- 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 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.
- 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).
- TCSPC time-correlated single-photon counting method
- 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).
- CPL 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).
- ⁇ l( ⁇ ) The measurements of ⁇ l( ⁇ ) 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( ⁇ ), therefore the photomultipliers used must be very efficient.
- the luminescence asymmetry factor In order to be able to compare the emission of circularly polarized light between fluorophores, the luminescence asymmetry factor should be used: where I( ⁇ ) 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.
- 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.
- 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.
- the ⁇ E ST is directly proportional to the orbital overlap between the HOMO and the LUMO of a molecule.
- 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.
- 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.
- TADF Thermally Activated Delayed Fluorescence
- 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.
- 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 fluorescence signal of the product obtained is compared with that of a reference of known ⁇ F emitting in a close wavelength range.
- said reference of known ⁇ F is coumarin 102.
- 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.
- 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).
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