WO2021159918A1 - 可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物 - Google Patents

可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物 Download PDF

Info

Publication number
WO2021159918A1
WO2021159918A1 PCT/CN2021/072344 CN2021072344W WO2021159918A1 WO 2021159918 A1 WO2021159918 A1 WO 2021159918A1 CN 2021072344 W CN2021072344 W CN 2021072344W WO 2021159918 A1 WO2021159918 A1 WO 2021159918A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecule
iii
chelate
composition
light
Prior art date
Application number
PCT/CN2021/072344
Other languages
English (en)
French (fr)
Inventor
耶尔森·哈特穆特
Original Assignee
四川知本快车创新科技研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 四川知本快车创新科技研究院有限公司 filed Critical 四川知本快车创新科技研究院有限公司
Priority to JP2022542356A priority Critical patent/JP2023511056A/ja
Priority to KR1020227023305A priority patent/KR20220120597A/ko
Priority to CN202180007152.2A priority patent/CN114929718A/zh
Priority to US17/794,947 priority patent/US20230354693A1/en
Publication of WO2021159918A1 publication Critical patent/WO2021159918A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a composition that uses cerium (III) chelate molecules as donors and fluorescent molecules as acceptors to perform non-radiative energy transfer to produce ultra-fluorescence with a small half-height width and short decay time, especially deep blue Color emission.
  • the blue, green or red luminescent fluorescent acceptor material after combining with the cerium (III) chelate molecule, can produce super-fluorescent emission with high color purity and short lifetime in the corresponding spectral range.
  • OLED has profoundly shaped or at least influenced screen technology and even some lighting technology.
  • OLEDs with phosphorescent materials.John Wiley&Sons.and Yersin,H.(Ed.).(2019).Highly efficient OLEDs :Materials based on thermally activated delayed fluorescence (High-efficiency OLED: based on thermally activated delayed fluorescent materials).
  • the solution to this problem is to ensure that all, that is, 100%, of the singlet or triplet excitons generated in the OLED light-emitting layer are captured by the thermally activated delayed fluorescence-based emitter, the so-called TADF emitter.
  • the solution to this color purity problem is to introduce an additional component, namely pure organic fluorescent molecule F, in addition to using a TADF emitter with a larger half-height width in the OLED light-emitting layer.
  • the fluorescence spectrum of this molecule has a FWHM that is significantly narrower than the TADF emitter (for example, less than 0.25 eV).
  • the fluorescent molecule F is suitable for non-radiative energy transfer through the Foerster energy transfer mechanism (dipole-to-dipole energy transfer), effectively eliminating TADF emission (donor) and effectively spontaneously generating fluorescence (acceptor) (Forster energy transfer mechanism is well known to those skilled in the art).
  • Foerster energy transfer mechanism dipole-to-dipole energy transfer
  • donor effectively eliminating TADF emission
  • acceptor effectively spontaneously generating fluorescence
  • the fluorescent molecule F has a high decimal molar extinction at the overlapping absorption band.
  • the coefficient ⁇ ( ⁇ >25000Lmol -1 cm -1 ).
  • the average distance between the TADF emitter and the fluorescent molecule F generally does not exceed 3 to 4 nm, but the case where the average distance between the TADF emitter and the fluorescent molecule F is less than 1 nm must be ruled out. The specific reasons will be discussed later. It can be seen that, according to this concept, a deep blue OLED with suitable color purity (CIE y component ⁇ 0.15) and good device efficiency (EQE close to 20%) can be obtained.
  • the method is generally referred to as the super-fluorescence mechanism.
  • 33-3 TADF Emitter Selection for Deep-Blue Hyper-Fluorescent OLEDs. In SID Symposium Digest of Technical Papers (Vol. 50, No. 1, pp. 466-469).] However, the use of TADF donor molecules and suitable acceptor molecules has so far only reached a limited device lifetime. [Baumann,T.,Budzynski,M.,&Kasparek,C.(2019,June).33-3:TADF Emitter Selection for Deep-Blue Hyper-Fluorescent OLEDs.In SID Symposium Digest of Technical Papers(Vol.50,No .1,pp.466-469).]
  • the stability of the OLED device can be significantly improved by shortening the emission decay time of the emitter.
  • the reason is that by shortening the emission attenuation of the emitter The time significantly reduces the chemical reaction or decomposition in the excited state.
  • shortening the emission decay time also significantly improves the roll-off behavior of the device (the device efficiency decreases as the current density or brightness increases).
  • the emission decay time of the TADF emitters known so far is relatively long, that is, about a few microseconds.
  • the combination of Ce(III) chelate (donor) and fluorescent acceptor molecule F eliminates the shortcomings of TADF decay time of a few microseconds, due to (radioactive) Ce(III) chelation
  • the object decay time is less than 100ns, which is more than 50 times shorter than the TADF emitters used so far.
  • the combination with the acceptor molecule F produces narrowband fluorescence after effective non-radiative energy transfer (according to the Foerster mechanism), that is, hyperfluorescence ( Figure 1).
  • the neutral Ce donor chelate used in the composition with the fluorescent molecule F is composed of Ce(III) central ion, which is eight-coordinated, preferably nine-coordinated or at most twelve Coordination is mainly coordinated by organic chelate ligands.
  • the ligand of the Ce donor chelate is preferably a two-coordinated or particularly preferably a three-coordinated chelate ligand.
  • the ligands include, for example, small organic aromatic rings or heteroaromatic ring systems, such as preferably monocyclic or bicyclic ring systems, which are suitable for capturing singlet or triplet excitons. This means that the lowest ligand excited singlet state S 1 (L) and the lowest ligand excited triplet state T 1 (L) are both occupied.
  • the ligand is chosen so that the lowest triplet state is higher in energy than the emission state of Ce(III).
  • the energy state to which it belongs can be easily determined by the current spectroscopic measurement method. The corresponding energy determination can also be obtained using quantum chemistry methods (for example, according to the TD-DFT method).
  • the Ce(III) chelate involved is neither a pure TADF type singlet trapping mechanism nor a pure triplet trapping mechanism, but a new exciton trapping mechanism involving double trapping. Put it into the fifth-generation OLED capture mechanism.
  • the capture mechanism of the fourth-generation OLED is described).
  • the donor chelate is, for example, a molecule of formula I or II.
  • R 1 pyrazolyl, triazolyl, heteroaryl, alkyl, aryl, alkoxy, phenol, amine, amide, these groups may be substituted or unsubstituted, or especially carbazole
  • the (Cz)- group is either a carbazole group substituted with one or two tert-butyl groups.
  • R 5 R 1 or H
  • R 2 , R 3 , R 4 , R 6 , R 7 H, halogen or hydrocarbon group which may contain heteroatoms, especially alkyl, aryl, and heteroaryl.
  • R 2 -R 7 may be fluorinated independently of each other, that is, have at least one F in particular.
  • the donor chelate is the following compound: Ce[pz 3 B(2,7-t-Bu 2 -Cz)] 3 , Ce[pz 3 B(3,6-t-Bu 2- Cz)] 3 or Ce[pz 3 B(4,5-t-Bu 2 -Cz)] 3 and a compound in which the carbazolyl group has only one tert-butyl group at any position. Also preferred are those substituted with one or two tert-butyl groups on one carbazolyl group or two carbazolyl groups. In the embodiment, it is also preferred that there is no tert-butyl chelate, that is, according to the following molecular formula Ce[pz 3 B(Cz)] 3 .
  • the use of the chelate compound of formula I or II in the light-emitting layer according to the present invention can obtain light-emitting devices with excellent properties.
  • an air-stable and soluble Ce chelate (a substance of formula I) is obtained.
  • a triazole group was used instead of a pyrazole group (the compound of formula II)
  • the desired performance was obtained.
  • the donor chelate used in the composition according to the present invention is, for example, a compound having a uniform substitution pattern at the boron atom, especially because it is easiest to synthesize such a compound.
  • the compound has the preferred formula III or IV.
  • the main advantage of the compounds is that they have good solubility in almost all polar solvents, such as H 2 O, MeOH, EtOH, MeCN, CHCl 3 , CH 2 Cl 2, etc., and good stability to water and oxygen. Therefore, the compound is quite suitable for spin coating, printing and/or inkjet printing processes.
  • the compound can also be applied using vacuum sublimation or vapor deposition.
  • Another major advantage is that it simplifies the synthesis of Ce chelate and does not need to be synthesized in a protective atmosphere and anhydrous solvent.
  • the chelate can also be changed by the substitution or change of the ligand, so there are many possibilities to modify or adjust the luminescence characteristics (such as transition energy, color, quantum efficiency, decay time, etc.).
  • the Ce center in these donor chelates preferably has at least 9 coordination. This prevents decomposition.
  • the substituent R 1 or R 5 at the boron atom is far away from the center of the chelate and therefore does not interfere with the coordination.
  • the solubility can be adjusted by these substituents.
  • R 1 is preferably pyrazolyl
  • R 5 may be H
  • R 5 is preferably a residue other than H.
  • R 5 is triazolyl.
  • residues R 2 , R 3 , R 4 , R 6 and R 7 are each independently selected from hydrogen, halogen or a hydrocarbon group which may optionally contain heteroatoms and/or be substituted.
  • the heteroatoms are particularly selected from O, S, N, P, Si, Se, F, Cl, Br and/or I.
  • the residues R 1 to R 7 may have 0 to 10, or preferably 0 to 5 heteroatoms. If a residue (e.g., R 5) is H, then R 5 does not have a hetero atom. In some embodiments, each of the residues R 1 to R 7 has at least 1, especially at least 2 heteroatoms.
  • the heteroatom may also be present in the skeleton of the substituent or as a part of the substituent.
  • the residues R 1 to R 7 are hydrocarbyl groups, and the hydrocarbyl groups have one or more substituents (functional groups).
  • Suitable substituents or functional groups are, for example, halogen (ie F, Cl, Br or I), alkyl (especially C 1 to C 20 , preferably C 1 to C 6 alkyl), aryl, O-alkyl, O - aryl, S- aryl, S- alkyl, P- 2 alkyl, P- 2 aryl, N- aryl or N- 2-alkyl 2.
  • halogen ie F, Cl, Br or I
  • alkyl especially C 1 to C 20 , preferably C 1 to C 6 alkyl
  • aryl O-alkyl, O - aryl, S- aryl, S- alkyl, P- 2 alkyl, P- 2 aryl, N- aryl or N- 2-alkyl.
  • at least one of the residues R 1 to R 7 contains at least one fluorine in order to increase the volatility of the chelate.
  • the hydrocarbyl group is preferably an alkyl, alkenyl, alkynyl, aryl or heteroaryl group, especially an alkyl, aryl or heteroaryl group.
  • alkyl (Alkyl-) or alkyl (Alk-) as used herein each independently preferably represents a C 1 -C 20 , especially a C 1 -C 6 hydrocarbon group.
  • aryl refers to an aromatic system, such as an aromatic ring containing 5 to 12 carbon atoms, where the carbon atoms may be substituted by heteroatoms (for example, by N, S, or O).
  • substituents R 2 , R 3 , R 4 , R 6 and R 7 are preferably hydrogen or halogen, that is, substituents that are not highly demanding in terms of space.
  • substituents that require less sterically are given, for example, in Formulas I and II.
  • the size of the aromatic or heteroaromatic group used in the organic ligand is preferably limited to a monocyclic or bicyclic ring system.
  • R is, for example, CH 3 CH 2 , CH 3 CH 2 CH 2 or CH 3 -CH-CH 3 .
  • Ce(III) donor chelate is Formula VI.
  • the emission of the Ce(III) donor chelate has a highest emission peak of about 440 nm, a half-maximum width (FWHM) of about 4000 cm -1 (0.5 eV), and a decay time of about 50 ns.
  • Photoluminescence quantum efficiency Approximately between 60% and 85%.
  • the highest emission peak of the chelate in the solution (ethanol) and powder state has approximately the same value.
  • the fluorescent acceptor molecule used as a composition together with the Ce(III) donor chelate compound according to the present invention is a pure organic compound, and the emission decay time is less than 10ns or better less than 2ns.
  • the absorption band of the acceptor must be within the emission region of the Ce(III) donor chelate, so there is a clear overlap between the donor emission and the acceptor absorption spectra.
  • Mechanism of effective non-radiative energy transfer It is also necessary that the decimal molar extinction coefficient ⁇ of the acceptor is greater than 20,000 or more preferably greater than 40,000 Lmol -1 cm -1 . Under the condition that the emission is blue, Foster The energy transfer radius is 3 to 4 nm.
  • the acceptor fluorescent molecule used for deep blue hyperfluorescence should produce such an emission whose emission maximum is in the range of about 420 to 480 nm or particularly preferably in the range of 450 to 470 nm, and the full width at half maximum (FWHM) is narrower than 0.25 or It is more preferably narrower than 0.2 or narrower than 0.18 eV.
  • emission quantum efficiency No donor molecules More than 70% or better than 90%.
  • the decimal molar extinction coefficient ⁇ can be easily determined with current absorption photometers.
  • the fluorescent acceptor is the molecule TBPe (Formula VII):
  • This compound is characterized by four tert-butyl groups. They are used to expand the spatial distance between the donor and the acceptor, and to a large extent avoid the short-range energy transfer process with a transfer radius of about 1 nm to the T 1 state of the acceptor based on the Deter mechanism. This is important because for normal fluorescent molecules (except for TADF molecules), occupying the T 1 state will cause excitons to be lost, because the T 1 state is due to transition forbidden rather than radiation inactivation.
  • fluorescent acceptor molecules for blue, green, and red emitting devices are used. Examples are as follows.
  • red light emitters acceptors
  • the hyperfluorescence-generating composition having Ce(III) donor component and fluorescent acceptor component or composed of Ce(III) donor component and fluorescent acceptor component can be used in the following devices, preferably in organic light-emitting diodes (OLED), light-emitting electrochemical cell (LEEC), OLED sensor (especially steam or gas sensor without hermetic shielding), organic light-emitting transistor or organic laser.
  • OLED organic light-emitting diodes
  • LEEC light-emitting electrochemical cell
  • OLED sensor especially steam or gas sensor without hermetic shielding
  • compositions having a Ce(III) donor component and a fluorescent acceptor component or a composition composed of a Ce(III) donor component and a fluorescent acceptor component in the OLED are particularly preferred to use a composition having a Ce(III) donor component and a fluorescent acceptor component or a composition composed of a Ce(III) donor component and a fluorescent acceptor component in the OLED.
  • the OLED device is composed of multiple well-matched thin layers. The corresponding embodiments have been disclosed many times and are therefore known to those skilled in the art.
  • the light-emitting layer includes donor and acceptor components, which can be processed in a solution manner (for example, dip coating, inkjet printing) by vacuum sublimation or vapor deposition.
  • the light-emitting layer has a host material whose lowest triplet state is higher in energy than the 2 D 3/2 state of Ce(III) ion or better than the S 1 (L ) And T 1 (L) state.
  • the corresponding host materials and their T 1 (host) and S 1 (host) energies are known to those skilled in the art.
  • the doping of the Ce(III) component is 99% to 10%, preferably 12 to 18% (weight percentage).
  • the doping of the acceptor component is between 5% and 0.5%, preferably 1%. This low concentration is necessary to minimize the loss of efficiency due to direct charge trapping or the formation of excitons directly on the acceptor, and also to avoid the short-range dexter energy transfer to the T 1 state of the acceptor to a large extent .
  • the preferred donor and/or acceptor components are substituted with tert-butyl groups with extended spacing (e.g. for donors: Formula I with a carbazolyl group R 1 substituted by tert-butyl groups and for example for Receptor: Formula VII).
  • the advantages of using the composition of the present invention surpass the prior art, especially in reducing the emission decay time of the generated superfluorescence, which is reduced by one to three orders of magnitude.
  • the service life of the device is greatly extended, especially for deep blue light emission.
  • the roll-off performance of the device can also be significantly reduced.
  • Figure 1 realizes the photophysical process of, for example, deep blue super-fluorescence emission through a dual capture mechanism.
  • the singlet and triplet excitons generated in the OLED light-emitting layer are both captured by the S 1 (L) state and T 1 (L) state of the Ce(III) chelate ligand.
  • the fast intramolecular energy transfer results in the lowest excited state being occupied by the 2 D 3/2 state in the Ce(III) chelate.
  • the decay time of its fluorescence radiation transition (without acceptor) to the 2 F 5/2 and 2 F 7/2 states is 50 to 100 ns.
  • This Ce(III) chelate is used as a donor, through fast fluorescence resonance Energy transfer mechanism (FRET) for example, the energy transfer to the S 1 state of the organic acceptor molecule deep blue fluorescence, and ultimately produces a fluorescent emission.
  • FRET fast fluorescence resonance Energy transfer mechanism
  • the organic acceptor molecule is selected so that it has a narrow half-height width (FWHM: for example ⁇ 0.2eV) and high photoluminescence quantum efficiency (E.g. 90%), and very short emission decay time (e.g. 2ns).
  • FWHM narrow half-height width
  • E.g. 90% high photoluminescence quantum efficiency
  • very short emission decay time e.g. 2ns.
  • DPFPO 2,8-bis(diphenylphosphinooxy)dibenzofuran
  • OLED light-emitting layer layer thickness 20nm
  • DPFPO 2,8-bis(diphenylphosphinooxy)dibenzofuran
  • DPFPO 2,8-bis(diphenylphosphinooxy)dibenzofuran
  • the structure of the OLED light-emitting layer layer thickness 20nm, body: 2,8-bis(diphenylphosphinooxy)dibenzofuran (DBFPO) doped with 18% of the compound according to formula VI and 1% of the compound according to formula VII Compound.
  • DPFPO 2,8-bis(diphenylphosphinooxy)dibenzofuran

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

一种具有极短衰减时间的超荧光含铈(III)螯合物的组合物，特别是用于OLED应用的分子组合物，其具有Ce(III)螯合物形式的中性供体，和中性荧光受体分子。使用该组合物可以产生具有非常短的发射衰减时间的纯色发光，尤其对于深蓝色发光区域。所述组合物利用了激发态双重捕获机制，其可以归为第五代有机发光二极管(OLED)以及其他光电器件。

Description

可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(III)螯合物 技术领域
本发明涉及以铈(III)螯合物分子为供体，荧光分子为受体，进行非辐射性能量转移的组合物，以产生半高宽度小、衰减时间短的超荧光，特别是产生深蓝色发射。
蓝色、绿色或红色发光的荧光受体材料在结合了铈(III)螯合物分子后，可以在其相应的光谱范围内产生色纯度高，寿命短的超荧光发射。
背景技术
OLED已经深刻地塑造或至少影响了屏幕技术，甚至部分照明技术。例如，在Yersin,H.(Ed.).(2008).Highly efficient OLEDs with phosphorescent materials(基于磷光的高效OLED).John Wiley&Sons.和Yersin,H.(Ed.).(2019).Highly efficient OLEDs:Materials based on thermally activated delayed fluorescence(高效OLED：基于热激活延迟荧光材料).John Wiley&Sons.中可以找到有关现有技术的概述。
然而仍有不足之处，特别是在发光层材料方面。尤其是蓝光发光材料，到目前为止，尚不能满足高效OLED器件所需的色彩纯度和足够的稳定性。此外，对于绿光发射体和红光发射体的色纯度要求也尚未完全满足。
解决这个问题的方法在于确保所有的，即100％的在OLED发光层中产生的单重态或三重态激子被基于热激活延迟荧光的发射体，即所谓的TADF发射体捕获。Yersin,H.(Ed.).(2019).Highly efficient OLEDs:Materials based on thermally activated delayed fluorescence(高效OLED：基于热激活延迟荧光材料).John Wiley&Sons.，H.Yersin,U.Monkowius,DE 10 2008 033563，2008年7月17日登记，Uoyama,H.,Goushi,K.,Shizu,K.,Nomura,H.,&Adachi,C.(2012).Highly efficient organic light-emitting diodes from delayed fluorescence(来自延迟荧光的高效有机发光二极管).Nature,492(7428),234-238。然而，这些材料通常显现出较宽半高宽4000cm -1(FWHM，0.5eV)的发射带。因此，例如最大发射峰位于深蓝区域的发光材料，在绿光区域也具有相当的强度，这样就导致不是深蓝色而是天蓝色发光。因此，对色纯度的改善，仍然饱受期待。
解决此色纯度问题的方法是除了在OLED发光层中使用半高宽较大的TADF发射体之外，再引入一附加组分，即纯有机荧光分子F。此分子的荧光光谱具有比TADF发射体明显更窄的半高宽(例如小于0.25eV)。而更重要的是，所述荧光分子F适合于通过Foerster能量转移机制(偶极对偶极的能量转移)的非辐射能量转移，有效消除TADF发射(供体)以及有效自发 产生荧光(受体)(Forster能量转移机制是本领域技术人员所熟知的)。例如在参考文献[Turro,N.(1978).Modern Molecular Photochemistry.Menlo Park,California:The Benjamin/Cummings Publishing Co.；Barltrop,J.A.,&Coyle,J.D.(1975).Excited states in organic chemistry.Wiley.；Baumann,T.,Budzynski,M.,&Kasparek,C.(2019,June).33‐3:TADF Emitter Selection for Deep‐Blue Hyper‐Fluorescent OLEDs.In SID Symposium Digest of Technical Papers(Vol.50,No.1,pp.466-469).]中对相应的条件予以讨论。对于该机理重要的是供体发射(此处：TADF发射)和受体吸收(此处：荧光分子F)的光谱具有较好的重叠，荧光分子F在重叠吸收带处具有高的十进制摩尔消光系数ε(ε>25000Lmol -1cm -1)。TADF发射体与荧光分子F之间的平均间距一般不超过3到4nm，但TADF发射体与荧光分子F之间的平均间距小于1nm的情况必须被排除，具体原因将在后面讨论。由此可见，按此概念可以获得具有合适的色纯度(CIE y成分<0.15)和良好的器件效率(EQE接近20％)的深蓝发光的OLED。所述方法通常被称为超荧光机理。[Adachi,C.(2013,June).37.1:Invited Paper:Third Generation OLED by Hyperfluorescence.In SID Symposium Digest of Technical Papers(Vol.44,No.1,pp.513-514).Oxford,UK:Blackwell Publishing Ltd.；Nakanotani,H.,Higuchi,T.,Furukawa,T.,Masui,K.,Morimoto,K.,Numata,M.,...&Adachi,C.(2014).High-efficiency organic light-emitting diodes with fluorescent emitters.Nature communications,5(1),1-7.；Han,S.H.,&Lee,J.Y.(2018).Spatial separation of sensitizer and fluorescent emitter for high quantum efficiency in hyperfluorescent organic light-emitting diodes.Journal of Materials Chemistry C,6(6),1504-1508.；Jang,J.S.,Han,S.H.,Choi,H.W.,Yook,K.S.,&Lee,J.Y.(2018).Molecular design of sensitizer to suppress efficiency loss mechanism in hyper-fluorescent organic light-emitting diodes.Organic Electronics,59,236-242.；Byeon,S.Y.,Lee,D.R.,Yook,K.S.,&Lee,J.Y.(2019).Recent Progress of Singlet‐Exciton‐Harvesting Fluorescent Organic Light‐Emitting Diodes by Energy Transfer Processes.Advanced Materials,31(34),1803714.；Baumann,T.,Budzynski,M.,&Kasparek,C.(2019,June).33‐3:TADF Emitter Selection for Deep‐Blue Hyper‐Fluorescent OLEDs.In SID Symposium Digest of Technical Papers(Vol.50,No.1,pp.466-469).]然而，使用TADF供体分子和合适的受体分子迄今为止只能达到有限的器件寿命。[Baumann,T.,Budzynski,M.,&Kasparek,C.(2019,June).33‐3:TADF Emitter Selection for Deep‐Blue Hyper‐Fluorescent OLEDs.In SID Symposium Digest of Technical Papers(Vol.50,No.1,pp.466-469).]
通过缩短发射体的发射衰减时间可以明显改善OLED器件的稳定性。[Noda,H.,Nakanotani,H.,&Adachi,C.(2018).Excited state engineering for efficient reverse intersystem  crossing.Science advances,4(6),eaao6910.]，原因在于，通过缩短发射体的发射衰减时间明显减少了在激发态的化学反应或者分解。此外缩短发射衰减时间也显著地改善了器件的滚降行为(随电流密度或亮度增加而出现的器件效率降低)。迄今为止所知的TADF发射体的发射衰减时间相对较长，即大约几微秒。因此存在一种需求，即相对于现有技术，明显缩短供体分子的发射衰减时间，这也就是本发明的任务。当然，类似于TADF发射体，在发光层产生的所有激子必须都被捕获。
发明内容
上述的缺点可以通过本发明加以改进。
令人意外的是，Ce(III)螯合物(供体)和荧光受体分子F的组合物消除了TADF衰减时间长为几微秒的缺点，原因是(放射性)Ce(III)螯合物衰减时间少于100ns，超过50倍地短于迄今为止所使用的TADF发射体。与受体分子F的组合在有效非辐射能量转移(根据Foerster机理)之后产生了窄带荧光，即超荧光(图1)。
供体
根据本发明用于与荧光分子F的组合物中的中性Ce供体螯合物由Ce(III)中心离子组成，Ce(III)中心离子是八配位，优选九配位或最多十二配位，主要由有机螯合物配体配位。
Ce供体螯合物的配体优选二配位的或者特别优选三配位的螯合配体。所述配体包括，例如小的有机芳环或杂芳环系，例如优选单环或双环系，这些环系适于捕获单重态或三重态激子。这意味着，最低的配体激发单重态S 1(L)以及最低的配体激发三重态T 1(L)均被占据。如此选择配体是为了使最低三重态在能量上高于Ce(III)的发射态。所属的能量态可以方便地用目前的光谱测量方法确定。相应的能量确定也可以用量子化学方法获得(例如根据TD-DFT方法)。
基于Ce(690cm -1)的高自旋轨道耦合常数，实现了配位态之间快速的S 1(L)→T 1(L)系间窜跃以及振动弛豫。然后同样的在分子内进行了快速的从T 1(L)态到Ce(III)中心的最低激发态的非辐射能量转移。在此涉及到一个自旋和宇称允许的 2D 2/3(5d*)态，有效而快速的5d→4f发射发生在了与其能量接近的 2F 5/2和 2F 7/2态(间距≈2000cm -1)，并伴随着50-100ns的衰减时间(不涉及受体分子)。(图1)Ce(III)中心处的这个跃迁是一个荧光辐射过程。所涉及的Ce(III)螯合物既非单纯的TADF类型的单重态捕获机制，也非单纯的三重态捕获机制，而是一种新的涉及双重捕获的新的激子捕获机制，可以将其归入第五代OLED的捕获机制。(Yersin,H.,Mataranga-Popa,L.,Czerwieniec,R.,&Dovbii,Y.(2019).Design of a New Mechanism beyond Thermally Activated Delayed Fluorescence toward Fourth Generation Organic  Light Emitting Diodes.Chemistry of Materials,31(16),6110-6116.)中描述了第四代OLED的捕获机制)。
在优选的实施方式中供体螯合物例如为式I或II的分子。
Figure PCTCN2021072344-appb-000001
其中：
R 1＝吡唑基，三唑基，芳杂基，烷基，芳基，烷氧基，苯酚基，胺基，酰胺基，这些基团可以是取代或未取代的，或者特别是咔唑(Cz)-基团或者是被一个或两个叔丁基取代的咔唑基团。
R 5＝R 1或者H,和
R 2,R 3,R 4,R 6,R 7＝H,卤素或者可以含杂原子的烃基,特别是烷基，芳基，杂芳基。为了提高化合物的挥发性，R 2-R 7可以彼此独立地氟化，即特别地具有至少一个F。
在优选的实施方式中供体螯合物为以下化合物：Ce[pz 3B(2,7-t-Bu 2-Cz)] 3,Ce[pz 3B(3,6-t-Bu 2-Cz)] 3或者Ce[pz 3B(4,5-t-Bu 2-Cz)] 3以及咔唑基仅带有一个在任意位置的叔丁基的化合物。同样优选的是在一个咔唑基或者两个咔唑基上有一个或两个叔丁基取代的物质。在实施方式中也优选没有叔丁基的螯合物，即按照下列分子式Ce[pz 3B(Cz)] 3。
令人惊讶的是，在发光层中依据本发明使用式I或II的螯合物可以获得具有出色性能的发光器件。通过不同于氢基的R1基，获得了空气稳定和可溶的Ce螯合物(式I的物质)。同时发现，当使用三唑基团代替吡唑基团时(式II的化合物)，获得了所期望的性能。
在另一优选的实施方式中,依据本发明的组合物中使用的供体螯合物,例如为，具有在硼原子处均配取代模式的化合物，特别是因为最容易合成获得这种化合物。在此种情况下，所述化合物具有优选的式III或IV。
Figure PCTCN2021072344-appb-000002
此处为四顺式吡唑基硼酸酯或四顺式三唑基硼酸酯配体。
所述化合物的主要优点是它们在几乎所有极性溶剂，例如在H 2O，MeOH，EtOH，MeCN，CHCl 3，CH 2Cl 2等中具有良好溶解性以及对水和氧气的良好稳定性。因此，所述化合物相当地适合于旋涂，印刷和/或喷墨印刷工艺。也可以使用真空升华或气相沉积法涂布所述化合物。另一个主要优点是简化了Ce螯合物的合成，不必在保护气氛及无水溶剂中进行合成。所述螯合物也可以通过配体的取代或改变进行变化，因此有多种可能性来修改或调控发光特性(例如过渡能量，颜色，量子效率，衰减时间等)。
这些供体螯合物中的Ce中心优选具有至少9配位。这样可以防止分解。硼原子处的取代基R 1或R 5远离螯合物中心，因此不会干扰配位。通过这些取代基可以调节溶解性。在R 1＝H时，如现有技术所描述，得到了微溶的螯合物。对于R 1取代基，依据本发明，例如R 1＝吡唑基，可获得可溶的化合物。因此获得了非常适合湿化学加工的物质，这是一项重要的技术优势。
R 1优选为吡唑基，R 5可以是H，优选R 5为不是H的残基。特别优选R 5为三唑基。
残基R 2，R 3，R 4，R 6和R 7(在式III和IV中)各自彼此独立选自氢，卤素或一种可任选含有杂原子和/或被取代的烃基。
杂原子特别地选自O，S，N，P，Si，Se，F，Cl，Br和/或I。残基R 1至R 7可以具有0至10个，或优选0至5个杂原子。如果一个残基(例如R 5)为H，则R 5不具有杂原子。在一些实施方式中，残基R 1至R 7各自具有至少1个，特别具有至少2个杂原子。所述杂原子也可以存在于取代基的骨架中或作为取代基的一部分存在。在一个实施方式中，残基R 1至R 7为烃基，该烃基具有一个或多个取代基(官能团)。合适的取代基或官能团例如为卤素(即F，Cl，Br或I)，烷基(尤其是C 1至C 20，优选C 1至C 6烷基)，芳基，O-烷基，O-芳基，S-芳基，S-烷基，P-烷基 2，P-芳基 2，N-烷基 2或N-芳基 2。在许多情况下，优选的是，残基R 1至R 7中至少一个残基包含至少一个氟，以增加螯合物的挥发性。
烃基优选为烷基，烯基，炔基，芳基或杂芳基，特别是烷基，芳基或杂芳基。
除非另有说明，本文所用的术语烷基(Alkyl-)或烷基(Alk-)分别独立地优选表示C 1-C 20，特别是C 1-C 6的烃基。术语芳基表示芳香系统，例如含5至12个碳原子数的芳香环，其中碳原子可以被杂原子取代(例如被N，S或O取代)。
所有的取代基R 2，R 3，R 4，R 6和R 7优选为氢或卤素，即在空间上要求不高的取代基。空间上要求较小的取代基的其他示例在例如式I和II中给出。
对于依据本发明的产生深蓝色超荧光的所述供体螯合物的应用，有机配体中使用的芳族或杂芳族基团的大小优选限于单环或双环系。
供体分子的其他优选实施方式示于式V，
Figure PCTCN2021072344-appb-000003
其中R是例如CH 3CH 2，CH 3CH 2CH 2或CH 3-CH-CH 3。
Ce(III)供体螯合物的另一个优选实施方式为式VI。
Figure PCTCN2021072344-appb-000004
所述的Ce(Ⅲ)供体螯合物的发射具有最高发射峰约440nm，半高宽(FWHM)大约4000cm -1(0.5eV)，衰减时间确定为大约50ns。，光致发光量子效率
Figure PCTCN2021072344-appb-000005
大约在60％到85％之间。螯合物在溶液(乙醇)和粉末状态下的最高发射峰具有大致相同的值。通过部分或完全氘化Ce(III)螯合物的配体，可以实现
Figure PCTCN2021072344-appb-000006
值及相应的OLED效率的增加。
受体
根据本发明的与Ce(III)供体螯合物一同作为组合物使用的荧光受体分子是纯有机化合物，发射衰减时间少于10ns或更好是少于2ns。所述受体的吸收带必须在Ce(III)供体螯合物发射区域内，因此呈现了明显的供体发射与受体吸收的光谱重叠，目的是为了实现根据弗斯特
Figure PCTCN2021072344-appb-000007
机制的有效的非辐射能量转移。此外必要的是，受体的十进制摩尔消光系数ε大于20,000或更好是大于40,000Lmol -1cm -1。在发射为蓝色的条件下，弗斯特
Figure PCTCN2021072344-appb-000008
能量转移半径为3到4nm。高效非辐射能量转移的条件为本领域技术人员已知的，并且可以在例如以下参考文献中找到[Turro,N.J.,&Photochemistry,M.M.(1978).Benjamin/Cummings.Menlo Park,CA,317-319.；Barltrop,J.A.,&Coyle,J.D.(1975).Excited states in organic chemistry.Wiley.；Baumann,T.,Budzynski,M.,&Kasparek,C.(2019,June).33‐3:TADF Emitter Selection  for Deep‐Blue Hyper‐Fluorescent OLEDs.In SID Symposium Digest of Technical Papers(Vol.50,No.1,pp.466-469).]。用于深蓝色超荧光的受体荧光分子应产生这样的发射，其发射最大值在约420至480nm范围内或特别优选在450至470nm的范围内，且半高宽(FWHM)窄于0.25或更好是窄于0.2或窄于0.18eV。此外，发射量子效率
Figure PCTCN2021072344-appb-000009
(没有供体分子)高于70％或更好是优于90％。
十进制摩尔消光系数ε可以方便地用目前的吸收光度计来确定。
在深蓝色发射的一个实施方案中，荧光受体是分子TBPe(式VII)：
Figure PCTCN2021072344-appb-000010
该化合物的特征在于四个叔丁基。它们用于扩大供体和该受体之间的空间距离，在很大程度上避免了依据Deter机制的到受体的T 1态的大约1nm转移半径的短程能量转移过程。这很重要，因为对于正常荧光分子(TADF分子除外)，占据T 1态会导致激子损失，原因在于T 1态因为跃迁禁阻而非辐射失活。
在深蓝色受体发射的另一个实施方案中，选择λ max＝458nm和
Figure PCTCN2021072344-appb-000011
的BPPyA分子(式VIII)
Figure PCTCN2021072344-appb-000012
在深蓝色发射荧光受体的另一个实施方案中选择了根据式IX的具有发射数据λmax＝456nm，FWHM＝0.18eV和CIE-y＝0.09的化合物。
Figure PCTCN2021072344-appb-000013
在其他实施方案中，使用了用于发射蓝色，绿色和红色的器件的其他荧光受体分子。实例如下。
蓝光发射体(受体)的其他实例：
Figure PCTCN2021072344-appb-000014
Figure PCTCN2021072344-appb-000015
绿光发射体实例(受体)：
Figure PCTCN2021072344-appb-000016
Figure PCTCN2021072344-appb-000017
红光发射体实例(受体)：
Figure PCTCN2021072344-appb-000018
Figure PCTCN2021072344-appb-000019
其他的合适的荧光受体分子实例：
Figure PCTCN2021072344-appb-000020
所提及的Ce(III)供体螯合物的合成和荧光受体分子的合成均是已知的。
具有Ce(III)供体组分和荧光受体组分或由Ce(III)供体组分和荧光受体组分组成的产生超荧光的组合物可用于以下器件，优选用于有机发光二极管(OLED)，发光电化学电池(LEEC)，OLED传感器(尤其是没有密封屏蔽的蒸汽或气体传感器)，有机发光晶体管或有机激光器中。
特别优选的是在OLED中应用具有Ce(III)供体组分和荧光受体组分或由Ce(III)供体组分和荧光受体组分组成的组合物。所述OLED器件由多个匹配良好的薄层组成。相应的实施例已经被公开很多次，因此是本领域技术人员已知的。
根据本发明，需注意在OLED的发光层中的各种成分掺杂。所述发光层包含供体和受体组分，可通过真空升华或气相沉积以溶液方式加工(例如浸涂，喷墨打印)实现。所述发光层有一个主体材料，其最低三重态在能量上高于Ce(III)离子的 2D 3/2态或更好高于Ce(III)螯合物的配体的S 1(L)和T 1(L)态。相应的主体材料及其T 1(主体)和S 1(主体)能量均为本领域技术人员已知的。Ce(III)组分的掺杂为99％至10％，优选为12至18％(重量百分比)。受体组分的掺杂在5％和0.5％之间，优选为1％。这种低浓度是必需的，是为了最小化由于直接电荷捕获或直接在受体上形成激子而造成的效率损失，也是为了在很大程度上避免短程dexter能量转移到受体的T 1态。基于这些原因，优选的供体和/或受体组分，例如被扩大间距的叔丁基所取代(例如对于供体：具有被叔丁基取代的咔唑基R 1的式I和例如对于受体：式VII)。
使用本发明的组合物的优点超过现有技术，尤其是在减少所产生的超荧光的发射衰减时间方面，减少了一到三个数量级。与现有技术相比大大延长了器件的使用寿命，尤其是对于深蓝色发光。此外，与现有技术相比，通过缩短发射衰减时间，还可以显着降低器件的滚降性能。
附图说明
图1通过双重捕获机制实现例如深蓝色超荧光发射的光物理过程。
OLED发光层中产生的单重态和三重态激子均被Ce(III)螯合物配体的S 1(L)态和T 1(L)态所捕获。快速分子内能量转移导致最低激发态被Ce(III)螯合物中的 2D 3/2态所占据。其向 2F 5/2和 2F 7/2态的荧光辐射跃迁(无受体)的衰减时间为50至100ns。这种Ce(III)螯合物作为供体，通过快速荧光共振的
Figure PCTCN2021072344-appb-000021
能量转移机制(FRET)将能量传递到例如深蓝色荧光的有机受体分子的S 1态，从而最终产生荧光发射。所选择的有机受体分子使其具有窄的半高宽(FWHM：例如<0.2eV)和较高的光致发光量子效率
Figure PCTCN2021072344-appb-000022
(例如90％)，和非常短的发射衰减时间(例如2ns)。根据Dexter机制的从 2D 3/2态到受体T 1态的非辐射短程能量转移被大大抑制。按照该方 法也可以产生绿色或红色超荧光。
具体实施方式
下面结合实施例对本发明做进一步的详细说明。
实施例1
OLED发光层的结构：层厚度20nm，主体：2,8-双(二苯基膦氧基)二苯并呋喃(DBFPO)掺杂有15％Ce[B(pz) 4] 3,pz＝吡唑基和1％BPPyA(式VIII)。
实施例2
OLED发光层的结构：层厚度20nm，主体：2,8-双(二苯基膦氧基)二苯并呋喃(DBFPO)掺杂有15％Ce[B(pz) 4] 3,pz＝吡唑基和1％的根据式IX的化合物。
实施例3
OLED发光层的结构：层厚度20nm，主体：2,8-双(二苯基膦氧基)二苯并呋喃(DBFPO)掺杂有15％Ce[B(pz) 3(Cz-tert-Butyl) 3],pz＝吡唑基和Cz-tert-Butyl＝被叔丁基取代的咔唑基，和1％的根据式VIII的化合物。
实施例4
OLED发光层的结构：层厚度20nm，主体：2,8-双(二苯基膦氧基)二苯并呋喃(DBFPO)掺杂有18％根据式VI的化合物和1％的根据式VII的化合物。

Claims (22)

  1. 分子，具有以下的结构式I或II，或者由以下的结构式I或II构成：
    Figure PCTCN2021072344-appb-100001
    其中：
    R 1＝吡唑基，三唑基，芳杂基，烷基，芳基，烷氧基，苯酚基，胺基，酰胺基，这些基团为取代或未取代的，R 5＝R 1或者H,和
    R 2,R 3,R 4,R 6,R 7＝H,卤素、烃基或者含杂原子的烃基,特别是烷基，芳基，杂芳基；优选R 2-R 7彼此独立地氟化，即特别地具有至少一个F。
  2. 根据权利要求1所述的分子，具有以下的结构或者由以下的结构式构成：
    Ce[pz 3B(Cz)] 3
    其中Cz＝咔唑基和pz＝吡唑基，
    其中任选Cz彼此独立地被一个或两个叔丁基在任意位置取代。
  3. 根据权利要求2所述的分子，具有或由根据下列的式结构构成：
    Ce[pz 3B(2,7-t-Bu 2-Cz)] 3，Ce[pz 3B(3,6-t-Bu 2-Cz)] 3，Ce[pz 3B(4,5-t-Bu 2-Cz)] 3,
    其中t-Bu＝叔丁基。
  4. 根据权利要求1所述的分子，具有以下的结构式III或IV，或者由以下的结构式III或IV构成：
    Figure PCTCN2021072344-appb-100002
    此处为四顺式吡唑基硼酸酯或四顺式三唑基硼酸酯配体。
  5. 根据权利要求4所述的分子，其中R 2，R 3，R 4，R 6和R 7各自彼此独立选自氢，卤素、或一种任选含有杂原子和/或被取代或未取代的烃基，杂原子特别地选自O，S，N，P，Si，Se，F，Cl，Br和/或I。
  6. 根据权利要求5所述的分子，其中R 2，R 3，R 4，R 6和R 7为氢或卤素。
  7. 分子，具有以下的结构式V或VI，或者由以下的结构式V或VI构成：
    Figure PCTCN2021072344-appb-100003
    其中R是CH 3CH 2，CH 3CH 2CH 2或CH 3-CH-CH 3。
  8. 根据权利要求1至7任意所述的分子，可选地，具有至少一个氘。
  9. 根据权利要求1至7任意所述的分子作为中性供体分子在与荧光受体分子组成的组合物中的应用。
  10. 组合物，组成包括：
    一种以权利要求1-8任一所述的分子为Ce(III)螯合物形式的中性供体分子，
    和
    一种荧光受体分子，特别是根据式VII至IX的化合物，
    Figure PCTCN2021072344-appb-100004
  11. 根据权利要求10所述的组合物，其中所述中性供体分子具有Ce(III)中心离子，其是八至十二配位，尤其是与有机配体配位。
  12. 根据权利要求11所述的组合物，其中所述有机配体是二配位或优选三配位螯合配体和/或所述有机配体的最低三重态能量上高于能量最低的的Ce(III)螯合物激发态。
  13. 根据权利要求10至12所述的组合物，其中所述有机配体具有一个或两个环的芳香族 或杂芳族环系，用于捕获单重态激子和三重态激子，因此最低的配体激发单重态S 1(L)以及最低的配体激发三重态T 1(L)均被占据，并且发生快速的S 1(L)到T 1(L)系间窜跃，随之通过分子内能量迅速转移到Ce(III)中心。
  14. 根据权利要求13所述的组合物，其中所述荧光受体分子具有：
    -所述受体的十进制摩尔消光系数大于20,000Lmol -1cm -1，
    -半高宽(FWHM)<0.25eV，尤其是<0.2eV，
    -具有发射量子效率
    Figure PCTCN2021072344-appb-100005
    尤其是>90％的发射，
    -发射衰减时间τ<10ns，特别是<2ns，和/或
    -发射峰的最大值在420nm至480nm区域内，特别是对于深蓝色光谱区域。
  15. 根据权利要求10至14所述的组合物用于制备光电器件，特别是选自有机发光二极管(OLED)，发光电化学电池(LEEC)，OLED传感器，有机发光晶体管和有机激光中的应用。
  16. 光电器件，具有根据权利要求1至9所述分子或者权利要求10到14所述的组合物。
  17. 根据权利要求16所述的光电器件，包括
    -基底
    -阳极和
    -阴极，其中所述阳极或阴极被施加到该基底上，和
    -至少一层发光层，其设置于阳极和阴极之间且具有所述权利要求1至9所述分子或者权利要求10到14所述的组合物。
  18. 根据权利要求17所述的光电器件，其中：在发光层中的所述Ce(III)螯合物供体分子的质量掺杂比占发光层的99％至10％，尤其为18％至12％。
  19. 根据权利要求18所述的光电器件，其中所述荧光受体分子的质量掺杂比占发光层的0.5％至5％，尤其为1％。
  20. 制备根据权利要求16至19所述的光电器件的方法，其中使用了根据权利要求1至9所述分子或者权利要求10到14所述的组合物。
  21. 一种将光电子器件中所有单重态和三重态激子完全捕获的方法，其中将权利要求1至9所述分子作为Ce(III)螯合物供体用于非辐射能量转移到荧光受体。
  22. 根据权利要求21所述的方法，其中通过使用一种发绿色或红色光的荧光受体分子，会产生寿命短，尤其是<10ns或>2ns，对于相应的光谱区域具有高色纯度的超荧光。
PCT/CN2021/072344 2020-02-10 2021-01-16 可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物 WO2021159918A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022542356A JP2023511056A (ja) 2020-02-10 2021-01-16 光電デバイスに適用可能で、デュアル捕獲機構と超短減衰時間を備えた超蛍光セリウム（ｉｉｉ）含有キレート
KR1020227023305A KR20220120597A (ko) 2020-02-10 2021-01-16 광전 소자용 이중 포획 메커니즘 및 초단 감쇠 시간을 갖는 초형광 세륨(iii) 함유 킬레이트
CN202180007152.2A CN114929718A (zh) 2020-02-10 2021-01-16 可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物
US17/794,947 US20230354693A1 (en) 2020-02-10 2021-01-16 Superfluorescent cerium (iii)-containing chelate applicable to photoelectric devices and having a dual capture mechanism and ultra-short decay time

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020103268.4A DE102020103268B8 (de) 2020-02-10 2020-02-10 Ce(III)-Komplexe, Zusammensetzung aufweisend Ce(III)-Komplexe, optoelektronische Vorrichtung, Verfahren zu deren Herstellung, Verfahren zum Dublett-Harvesting und Verfahren für Hyperfluoreszenz mit sehr kurzer Abklingzeit
DEDE102020103268.4 2020-02-10

Publications (1)

Publication Number Publication Date
WO2021159918A1 true WO2021159918A1 (zh) 2021-08-19

Family

ID=76968550

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/072344 WO2021159918A1 (zh) 2020-02-10 2021-01-16 可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物

Country Status (6)

Country Link
US (1) US20230354693A1 (zh)
JP (1) JP2023511056A (zh)
KR (1) KR20220120597A (zh)
CN (1) CN114929718A (zh)
DE (1) DE102020103268B8 (zh)
WO (1) WO2021159918A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023156886A1 (ja) * 2022-02-18 2023-08-24 株式会社半導体エネルギー研究所 有機金属錯体、発光デバイス、発光装置、電子機器および照明装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023194363A1 (en) * 2022-04-04 2023-10-12 Beeoled Gmbh Metal-organic coordination compound comprising cerium(iii)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012124820A1 (ja) * 2011-03-15 2012-09-20 住友化学株式会社 金属錯体及び該金属錯体を含む有機電子素子
WO2012161205A1 (ja) * 2011-05-25 2012-11-29 住友化学株式会社 セリウム錯体及び該セリウム錯体を含む有機電子素子
JP2012246230A (ja) * 2011-05-25 2012-12-13 Sumitomo Chemical Co Ltd セリウム錯体及び該セリウム錯体を含む有機電子素子
WO2019122155A1 (en) * 2017-12-22 2019-06-27 Novaled Gmbh Semiconducting material, a method for preparing the same and electronic device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006048202A1 (de) * 2006-10-11 2008-04-17 Universität Regensburg Lanthanoid-Emitter für OLED-Anwendungen
CN101260295A (zh) 2008-04-22 2008-09-10 中山大学 一种发光稀土金属配合物及其制备的可调性发光纳米薄膜
DE102008033563A1 (de) 2008-07-17 2010-01-21 Merck Patent Gmbh Komplexe mit kleinen Singulett-Triplett-Energie-Abständen zur Verwendung in opto-elektronischen Bauteilen (Singulett-Harvesting-Effekt)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012124820A1 (ja) * 2011-03-15 2012-09-20 住友化学株式会社 金属錯体及び該金属錯体を含む有機電子素子
WO2012161205A1 (ja) * 2011-05-25 2012-11-29 住友化学株式会社 セリウム錯体及び該セリウム錯体を含む有機電子素子
JP2012246230A (ja) * 2011-05-25 2012-12-13 Sumitomo Chemical Co Ltd セリウム錯体及び該セリウム錯体を含む有機電子素子
WO2019122155A1 (en) * 2017-12-22 2019-06-27 Novaled Gmbh Semiconducting material, a method for preparing the same and electronic device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023156886A1 (ja) * 2022-02-18 2023-08-24 株式会社半導体エネルギー研究所 有機金属錯体、発光デバイス、発光装置、電子機器および照明装置

Also Published As

Publication number Publication date
KR20220120597A (ko) 2022-08-30
CN114929718A (zh) 2022-08-19
JP2023511056A (ja) 2023-03-16
DE102020103268B4 (de) 2023-02-23
DE102020103268A1 (de) 2021-08-12
DE102020103268B8 (de) 2023-04-20
US20230354693A1 (en) 2023-11-02

Similar Documents

Publication Publication Date Title
Katkova et al. Coordination compounds of rare-earth metals with organic ligands for electroluminescent diodes
Fan et al. Host and dopant materials for idealized deep‐red organic electrophosphorescence devices
EP2007780B1 (en) Light-emitting material
Cao et al. A novel D–π–A blue fluorophore based on [1, 2, 4] triazolo [1, 5-a] pyridine as an electron acceptor and its application in organic light-emitting diodes
WO2010093176A2 (en) Iridium complex and organic light-emitting diodes
JP2008013700A (ja) 発光材料及び発光素子
WO2021159918A1 (zh) 可用于光电器件的具有双重捕获机制和超短衰减时间的超荧光含铈(iii)螯合物
Tagare et al. Efficient near ultraviolet emissive (CIE y< 0.06) organic light-emitting diodes based on phenanthroimidazole–alkyl spacer–carbazole fluorophores: experimental and theoretical investigation
CN110372756B (zh) 一种二价铂络合物及其制备方法和应用
CN111725434A (zh) 有机电致发光器件
Chen et al. High thermal-stability benzocarbazole derivatives as bipolar host materials for phosphorescent organic light-emitting diodes
CN112125932B (zh) 一种二价铂配合物及其应用
CN110551157A (zh) 一种二价铂配合物及其制备方法和应用
CN116368957A (zh) 有机电致发光器件
Huh et al. Control of the horizontal dipole ratio and emission color of deep blue tetradentate Pt (II) complexes using aliphatic spacer groups
Zhao et al. A periphery hindered strategy with a dopant and sensitizer for solution-processed red TSF-OLEDs with high color purity
Lin et al. New high-T g bipolar benzimidazole derivatives in improving the stability of high-efficiency OLEDs
Yu et al. Sky-blue-emitting cationic iridium complexes with carbazole-type counter-anions and their use for efficient solution-processed organic light-emitting diodes
WO2013045402A1 (en) Light emitting material
Girase et al. Unipolar 1-phenylimidazo [1, 5-a] pyridine: a new class of ultra-bright sky-blue emitters for solution-processed organic light emitting diodes
Zeng et al. Geometric isomers of asymmetric rigid four-membered chelating ring based deep-red-emitting iridium complexes featuring three charged (0,− 1,− 2) ligands
Youn et al. Blue thermally activated delayed fluorescence emitters with a δ-pyridoindole donor moiety
Hu et al. An oxadiazole-functionalized ligand and its yellow-emitting Re (I) complex for organoelectronic application
JP7214142B2 (ja) 一重項分裂材料、三重項増感剤、化合物および薄膜
Huang et al. Donor-modified multiple resonance emitters with accelerated reverse intersystem crossing towards high-efficiency and narrowband deep-blue OLEDs

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21754529

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20227023305

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2022542356

Country of ref document: JP

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 21754529

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 21754529

Country of ref document: EP

Kind code of ref document: A1