CN114560880B - Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof - Google Patents

Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof Download PDF

Info

Publication number
CN114560880B
CN114560880B CN202210204059.7A CN202210204059A CN114560880B CN 114560880 B CN114560880 B CN 114560880B CN 202210204059 A CN202210204059 A CN 202210204059A CN 114560880 B CN114560880 B CN 114560880B
Authority
CN
China
Prior art keywords
added
fluorescent material
thermal activation
activation delay
reaction
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN202210204059.7A
Other languages
Chinese (zh)
Other versions
CN114560880A (en
Inventor
李贵杰
佘远斌
湛丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Hongwu Technology Co ltd
Original Assignee
Zhejiang Hongwu Technology Co ltd
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 Zhejiang Hongwu Technology Co ltd filed Critical Zhejiang Hongwu Technology Co ltd
Priority to CN202210204059.7A priority Critical patent/CN114560880B/en
Publication of CN114560880A publication Critical patent/CN114560880A/en
Application granted granted Critical
Publication of CN114560880B publication Critical patent/CN114560880B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • 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
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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
    • 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

Landscapes

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

Abstract

The invention provides an organic thermal activation delay fluorescent material constructed by a phenol oxygen-pyridine chelate boron difluoride receptor and application thereof, wherein a donor-receptor framework can realize smaller HOMO and LUMO overlapping, and delta E is reduced S1‑T1 The method is beneficial to improving the speed of the cross-over between reverse systems and realizing high-efficiency luminescence. The thermal activation delay fluorescent material is shown in a general formula (1) or (2):

Description

Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof
Technical Field
The invention relates to a thermal-activation delayed fluorescence material and application thereof, belongs to the field of organic luminescent materials, and in particular relates to a thermal-activation delayed fluorescence organic luminescent material containing a phenoloxy-pyridine chelate boron difluoride receptor structural unit and an organic electroluminescent device containing the thermal-activation delayed fluorescence organic luminescent material.
Background
Organic Light-Emitting diodes (OLEDs) have been developed in recent years, and compared with LCD display technology, OLEDs have the following advantages: the LED lamp emits light autonomously, a backlight source is not needed, and energy is saved; foldable or bendable; the response speed is high, and the contrast ratio is high; the working temperature range is wide; materialLow cost, high luminous efficiency, etc. OLED has become a new generation of full-color display and lighting technology, receiving widespread attention from academia and industry, and has found wide application in flat panel displays, solid state lighting, military and aerospace applications, and is expected to replace liquid crystal displays (Liquid Crystal Display, LCDs) in the future. In the early development stage of the OLED, the traditional organic small molecule fluorescent material is mainly adopted, and the material has good device stability. However, at most, 25% of singlet excitons can be theoretically utilized, and the rest 75% of triplet excitons can only be deactivated through non-radiative transition due to transition inhibition, so that the application of the triplet excitons in the OLED is limited. The second generation phosphorescence material can break triplet state transition forbidden resistance due to spin orbit coupling effect (SOC) of heavy metal, can effectively promote intersystem crossing of electrons from singlet state to triplet state, and fully utilizes all singlet state and triplet state excitons generated by electric excitation to ensure that the maximum theoretical quantum efficiency reaches 100 percent. Phosphorescent materials often require the introduction of extremely expensive rare heavy metals, which are costly to produce and have limited reserves of noble metals, limiting the development of second generation OLED devices. The university of September, adachhi, then teaches the synthesis of a series of thermally activated delayed fluorescence (TADF, thermally activated delayed fluorescence) materials for the donor-acceptor framework, which are designed to achieve spatial separation of HOMO and LUMO with less overlap of HOMO and LUMO and less singlet and triplet energy level differences ΔE S1-T1 . Under the excitation of heat in the surrounding environment, the reverse intersystem crossing (RISC) from the lowest triplet excited state (T1) to the lowest singlet excited state (S1) can be realized, so that the triplet excitons are effectively utilized to generate delayed fluorescence, and the theoretical internal quantum efficiency can also reach 100%. The TADF material has the greatest advantages that the pure organic material is adopted, the use of metal organic complex containing noble metal is avoided, the application prospect in the OLED field is huge, and the OLED based on the TADF has great progress. However, the design of high efficiency TADF materials with long lifetime and high brightness remains challenging, and organoboron compounds have unique optical and electronic properties, are widely studied and used as organic optoelectronic materials, and are expected to achieve high efficiency and stable luminescence, solving the above-mentioned problems. At the same time, novel efficient blueThe design and development of photo-thermally delayed fluorescent materials is also a significant problem in the field of OLEDs.
Disclosure of Invention
The invention aims to provide a donor-acceptor type heat-activated delayed fluorescent material constructed based on a phenoxy-pyridine chelate boron difluoride acceptor structural unit, which can be used in the fields of OLED display and illumination.
The chemical formula of the compound is shown as a general formula (1) or (2):
wherein,
in the formula (1), R a1 、R b1 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 An aryloxy group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m 1 、n 1 r is respectively a1 And R is b1 Is the number of (3); wherein m is 1 Is an integer of 0 to 4, n 1 An integer of 0 to 3;
in the formula (2), R a2 、R b2 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 An aryloxy group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m 2 、n 2 r is respectively a2 And R is b2 Is the number of (3); m is m 2 Is an integer of 0 to 4, n 2 An integer of 0 to 3;
donor D 1 、D 2 Each independently is one of the following structures:
wherein,
R 1 、R 2 、R 3 、R 4 、R 7 、R 8 、R 10 、R 11 、R 12 、R 13 、R 14 and R is 15 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 Aryloxy, halogen, silicon-based, mono-or di-alkylamino, mono-or di-arylamino, cyano, or combinations thereof, wherein two adjacent substituents may be fused to form a ring;
o 1 、p 1 、q 1 、r 1 、s 1 、t 1 、u 1 、v 1 、w 1 、x 1 、y 1 and z 1 R is respectively 1 、R 2 、R 3 、R 4 、R 7 、R 8 、R 10 、R 11 、R 12 、R 13 、R 14 And R is 15 Is the number of (3);
o 1 and p 1 Is an integer of 0 to 5; q 1 、r 1 、s 1 、t 1 、u 1 、v 1 、w 1 、x 1 、y 1 And z 1 Is an integer of 0 to 4.
Further, the structural formula of the thermally activated delayed fluorescence material may be preferably as shown in (3) and (4):
wherein,
in the formula (3), R a3 、R b3 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 An aryloxy group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m 3 、n 3 r is respectively a3 And R is b3 Is the number of (3); wherein m is 3 Is an integer of 0 to 4, n 3 An integer of 0 to 3;
in the formula (4), R a4 、R b4 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 An aryloxy group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m 4 、n 4 r is respectively a4 And R is b4 Is the number of (3); m is m 4 Is an integer of 0 to 4, n 4 An integer of 0 to 3;
said donor D 3 Is one of the following structures:
wherein,
R 1' 、R 2' 、R 3' 、R 4' 、R 7' 、R 8' 、R 10' 、R 11' 、R 12' 、R 13' 、R 14' and R is 15' Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 Aryloxy, halogen, silicon-based, mono-or di-alkylamino, mono-or di-arylamino, cyano, or combinations thereof, wherein two adjacent substituents may be fused to form a ring;
o 2 、p 2 、q 2 、r 2 、s 2 、t 2 、u 2 、v 2 、w 2 、x 2 、y 2 and z 2 R is respectively 1’ 、R 2’ 、R 3’ 、R 4’ 、R 7’ 、R 8’ 、R 10’ 、R 11’ 、R 12’ 、R 13’ 、R 14’ And R is 15’ Is the number of (3);
o 2 and p 2 Is an integer of 0 to 5; q 2 、r 2 、s 2 、t 2 、u 2 、v 2 、w 2 、x 2 、y 2 And z 2 Is an integer of 0 to 4.
Further, the thermally activated delayed fluorescence material according to the present invention is preferably one of the following structures:
the term "heteroaryl" as used herein includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (1, 2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl and 1,3, 4-oxadiazolyl) piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazolyl, 1,2,4, 5-tetrazolyl, 1,2, 3-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, thiazolyl, thienyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazolyl, 1,3, 4-triazolyl, and the like.
The term "silyl" as used herein is defined by the formula-SiR 1 R 2 R 3 Represented by R, wherein 1 ,R 2 And R is 3 Can be independently hydrogen or alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups as described herein.
"R" as used in the present invention a1 ,”“R a2 ,”“R a3 ,”“R an "(where n is an integer) may independently have one or more of the recited groups. For example, if R 1 Is a straight chain alkyl group, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxy, alkoxy, alkyl, halogen, and the like. Depending on the selected groups, the first group may be incorporated within the second group, or alternatively, the first group may be pendant (i.e., linked) to the second group.
The compounds of the present invention may contain an "optionally substituted" moiety. Generally, the term "substituted" (whether the term "optional" is present or not in the foregoing) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. Combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, unless expressly indicated to the contrary, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted).
The structure of the compound can be represented by the following formula:
it is understood to be equivalent to the following formula:
where m is typically an integer. Namely, R a Is understood to mean five individual substituents R a(1) ,R a(2) ,R a(3) ,R a(4) ,R a (5) . "individual substituents" means each R a The substituents may be independently defined. For example, if R in one case a(1) Halogen, then in this case R a(2) Not necessarily halogen.
In the present invention, the thermally activated delayed fluorescence material based on the chelate of a phenoxy-pyridine to boron difluoride acceptor building block is electrically neutral.
The thermal activation delay fluorescent material containing the phenoloxy-pyridine chelate boron difluoride receptor structure unit provided by the invention can be used for various purposes, can be used as a luminescent material of an organic electroluminescent device, can be used as a main material or other functional layer materials, and can be applied to full-color displays, lighting devices and the like.
The present invention relates to an optical or electro-optical device comprising one or more of the above-described thermally activated delayed fluorescence materials comprising a phenoxy-pyridine chelate boron difluoride acceptor building block.
Compared with the prior art, the invention has the beneficial effects that:
in the TADF material of the structural unit of the phenol oxygen-pyridine chelate boron difluoride acceptor, boron atoms are connected with phenol groups, and an empty p orbit is coordinated with a lone pair electron pair on pyridine N atoms to form a stable four-coordination structure. The tetra-coordinated boron compounds have good chemical and thermal stability, especially compounds containing B-O and B-F bonds due to their high bond dissociation energies (536 and 613kJ/mol, respectively). Coordination of phenol-group chelated boron difluoride and pyridine, and electronic delocalization to be integralAnd (3) a conjugated system, so that pi electron accepting capability of pyridine is improved, and then molecules with donor-acceptor structures are constructed by introducing electron donating groups with pi conjugated systems, intramolecular charge transfer (ICT, intramolecular Charge Transfer) is promoted, and a TADF effect is obtained. In addition, a rigid pi conjugated framework with a parallel ring structure can be formed, so that energy loss caused by vibration coupling can be effectively restrained, and the luminous quantum efficiency is improved. The introduction of substituent between electron acceptor and donor can regulate the dihedral angle between acceptor effectively, break conjugate and realize spectrum blue shift. And can also realize different degrees of separation of HOMO and LUMO, and can obtain smaller delta E S1-T1 And realizing TADF luminescence. The TADF material of the phenoloxy-pyridine chelated boron difluoride receptor structural unit has strong luminous efficiency and higher carrier mobility, the photoelectric performance of the TADF material is strongly dependent on ligand properties, and the photophysical properties of the TADF material can be effectively regulated and controlled through ligand design, so the TADF material is a very promising luminescent material.
Drawings
FIG. 1 is the emission spectra of toluene solutions of the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2, respectively, at room temperature.
FIG. 2 is an emission spectrum of DEPEO films of luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 at room temperature.
FIG. 3 is a plot of DEPEO film luminescence decay (normalized luminescence intensity versus time) for luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2, and m-PhCz-BF 2.
FIG. 4 is an electroluminescent spectrum of a device with a luminescent material p-Cz-BF2 as a light emitter doped differently in different proportions of the dual host material and with electron transport materials.
Fig. 5 is a graph of current density vs. voltage vs. luminous intensity for a device with a different proportion of a bi-host material and a different doping of an electron transport material with a luminescent material p-Cz-BF2 as a light emitter.
Fig. 6 is a graph of external quantum efficiency versus current density for a device with different proportions of the dual host material and different doping of the electron transport material with the luminescent material p-Cz-BF2 as the emitter.
FIG. 7 is an electroluminescent spectrum of a device with a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
Fig. 8 is a plot of device current density versus voltage versus luminous intensity for a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
Fig. 9 is a graph of external quantum efficiency versus current density for a device with a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
Detailed Description
The following examples, which are merely exemplary of the present disclosure and do not limit the scope of the claims, provide one of ordinary skill in the art with a means of making and evaluating the compounds described herein and their OLED devices. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise indicated, temperature is in units of degrees celsius or at ambient temperature and pressure is at or near atmospheric pressure.
The methods described in this example for preparing the disclosed compounds described herein are one of many, and many others are possible for preparing the disclosed compounds of this application, and this application is not intended to be limiting. Accordingly, one skilled in the art to which this disclosure pertains may readily modify the methods recited or utilize different methods to prepare one or more of the disclosed compounds. The following methods are merely exemplary, temperature, catalyst, concentration, reactant composition, and other process conditions may vary, and for the desired compounds, one of ordinary skill in the art can readily select appropriate reactants and conditions for preparation.
On Varian Liquid State NMR instrument 1 H and 13 c NMR spectrum test. The solvent is CDCl 3 Or DMSO-d 6 . The solvent is internally provided with an internal standard tetramethylsilane, and the chemical shift refers to tetramethylsilane (delta=0.00 ppm); otherwise, if CDCl is used 3 Is soluble in waterThe agent is used for preparing the medicine, 1 h NMR spectrum chemical shift was then referenced to residual solvent (δ=7.26 ppm); if using DMSO-d 6 Is used as a solvent, and is not limited by the solvent, 1 the chemical shift of the H NMR spectrum is then referred to the residual solvent H 2 O (δ=3.33 ppm). The nuclear magnetic data in the examples are explained using the following abbreviations (or combinations thereof) 1 Multiplicity of H NMR: s=singles, d=doubles, t=triples, q=quadruples, p=quintuples, m=multiplets, br=broad.
Preparation example
Example 1: the luminescent material p-Cz-BF2 may be synthesized as follows:
synthesis of intermediate p-Cz-OMe: 1-Br (2.10 g,7.95mmol,1.0 eq), carbazole (1.60 g,9.54mmol,1.2 eq.), sodium tert-butoxide (1.91 g,19.88mmol,2.5 eq.) and Pd were successively added to a 100mL three-necked flask 2 (dba) 3 (220 mg,0.24mmol,0.03 eq.) and XPhos (229 mg,0.48mmol,0.06 eq.) then nitrogen was purged three times and toluene (35 mL) was added by injection and reacted at 120℃for 70 hours in an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/ethyl acetate=20:1-5:1, yielding 2.63g of a yellowish brown solid in 94% yield. 1 H NMR(500MHz,CDCl 3 )δ3.90(s,3H),7.23(d,J＝2.0Hz,1H),7.28-7.37(m,4H),7.43-7.46(m,2H),7.53(d,J＝8.5Hz,2H),7.82-7.87(m,1H),7.97(dt,J＝8.0,1.0Hz,1H),8.04(d,J＝8.0Hz,1H),8.16(dt,J＝8.0,1.0Hz,2H),8.80(d,J＝4.5Hz,1H)。
Synthesis of intermediate p-Cz-OH: to a dry 250mL three-necked flask was added p-Cz-OMe (2.98 g,8.51mmol,1.0 eq.) and dried dichloromethane (100 mL). Boron tribromide (1.61 mL,17.03mmol,2.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 10 hours. Quenching with sodium bicarbonate solution, extracting with dichloromethane three times, mixing the organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, and purifying the crude product with silica gel columnSpectrum separation, eluting agent: petroleum ether/dichloromethane=20:1-5:1, yielding 1.82g of yellow solid with 64% yield. 1 H NMR(500MHz,DMSO-d 6 )δ7.17(d,J＝2.0Hz,1H),7.20(dd,J＝8.5,2.0Hz,1H),7.30-7.33(m,2H),7.45-7.54(m,5H),8.10(td,J＝8.0,2.0Hz,1H),8.26(d,J＝7.7Hz,2H),8.33(d,J＝8.5Hz,2H),8.70(dd,J＝5.0,1.0Hz,1H),14.58(s,1H)。
Synthesis of luminescent material p-Cz-BF 2: in a dry 250mL three-necked flask, p-Cz-OH (1.82 g,5.41mmol,1.0 eq.) and methylene chloride (100 mL) were added, then boron trifluoride diethyl ether (6.8 mL,54.1mmol,10 eq.) was added at-15℃and the reaction was stirred at room temperature for 10 hours, then N, N-diisopropylethylamine (14.2 mL,81.15mmol,15 eq.) was added and the reaction continued for 11 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:3, yielding 1.75g of a yellowish green solid with a yield of 84%. 1 H NMR(500MHz,DMSO-d 6 )δ7.32-7.35(m,2H),7.39(d,J＝2.0Hz,1H),7.43(dd,J＝8.5,2.0Hz,1H),7.47-7.50(m,2H),7.57(d,J＝8.0Hz,2H),7.90-7.93(m,1H),8.27(dt,J＝8.0,1.0Hz,2H),8.52(d,J＝8.5Hz,1H),8.54-8.58(m,1H),8.71(d,J＝8.5Hz,1H),8.83(d,J＝6.0Hz,1H)。
Example 2: the luminescent material p-PhCz-BF2 can be synthesized as follows:
synthesis of intermediate p-PhCz-OMe: 1-Br (2.0 g,7.57mmol,1.0 eq), phenylcarbazole (2.66 g,8.33mmol,1.1 eq.), sodium tert-butoxide (1.82 g,18.93mmol,2.5 eq.) and Pd were successively added to a 100mL three-necked flask 2 (dba) 3 (208 mg,0.23mmol,0.03 eq.) and XPhos (217 mg,0.45mmol,0.06 eq.) then nitrogen was purged three times and toluene (40 mL) was added by injection and reacted at 125℃in an oil bath for 72 hours. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the organic phases combined, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressureRemoving the solvent by distillation, separating the crude product by silica gel column chromatography, eluting with a eluting agent: petroleum ether/dichloromethane=20:1-1:1, giving 2.76g of brown solid in 73% yield. 1 H NMR(400MHz,CDCl 3 )δ3.93(s,3H),7.28(d,J＝2.0Hz,1H),7.35–7.41(m,4H),7.50(t,J＝7.6Hz,4H),7.61(d,J＝8.4Hz,2H),7.71–7.77(m,6H),7.89(t,J＝7.6Hz,1H),8.00(d,J＝8.0Hz,1H),8.07(d,J＝8.0Hz,1H),8.42(d,J＝1.6Hz,2H),8.82(d,J＝4.4Hz,1H)。
Synthesis of intermediate p-PhCz-OH: to a dry 250mL three-necked flask was added p-PhCz-OMe (2.76 g,5.49mmol,1.0 eq.) and dried dichloromethane (60 mL). Boron tribromide (1.04 mL,10.98mmol,2.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 20 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting with: petroleum ether/dichloromethane=20:1-1:1, yielding 2.14g of yellow solid with 80% yield. 1 H NMR(500MHz,DMSO-d 6 )δ7.24(d,J＝2.0Hz,1H)7.27(dd,J＝8.5,2.0Hz,1H),7.35–7.39(m,2H),7.49–7.53(m,5H),7.63(d,J＝8.5Hz,2H),7.82–7.85(m,6H),8.11(td,J＝8.0,2.0Hz,1H),8.35–8.38(m,2H),8.71(ddd,J＝5.0,2.0,1.0Hz,1H),8.76(d,J＝1.5Hz,2H),14.64(s,1H)。
Synthesis of luminescent material p-PhCz-BF 2: in a dry 100mL three-necked flask was added p-PhCz-OH (2.0 g,4.09mmol,1.0 eq.) and methylene chloride (50 mL), then boron trifluoride diethyl ether (5.2 mL,40.93mmol,10 eq.) was added at-15℃and the reaction was stirred at room temperature for 20 hours, then N, N-diisopropylethylamine (10.72 mL,61.35mmol,15 eq.) was added and the reaction continued for 24 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:3, yielding 1.94g of a yellowish green solid with a yield of 88%. 1 H NMR(400MHz,Chloroform-d)δ7.35–7.41(m,3H),7.48–7.54(m,5H),7.65–7.75(m,9H),8.09(d,J＝8.4Hz,1H),8.20–8.29(m,2H),8.40(s,2H),8.79(d,J＝6.0Hz,1H).
Example 3: the luminescent material p-tBuCz-BF2 can be synthesized as follows:
synthesis of intermediate p-tBuCz-OH: into a 50mL three-necked flask, 2-Br (400 mg,1.60mmol,1.0 eq), 3, 6-di-tert-butylcarbazole (581 mg,2.08mmol,1.3 eq), sodium tert-butoxide (384 mg,4.0mmol,2.5 eq), pd were successively added 2 (dba) 3 (44 mg,0.048mmol,0.03 eq.) and XPhos (92 mg,0.19mmol,0.12 eq.) then nitrogen was purged three times and toluene (18 mL) was added by injection and reacted at 120℃in an oil bath for 96 hours. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/dichloromethane=20:1-3:1, yielding 234mg of white solid in 33% yield. 1 H NMR(500MHz,CDCl 3 )δ1.47(s,18H),7.14(dd,J＝8.5,2.0Hz,1H),7.27(d,J＝2.0Hz,1H),7.30(ddd,J＝7.5,5.0,1.0Hz,1H),7.48(dd,J＝9.0,2.0Hz,2H),7.53(d,J＝8.5Hz,2H),7.88-7.91(m,1H),7.97-8.00(m,1H),8.14(d,J＝1.0Hz,2H),8.56(ddd,J＝5.0,2.0,1.0Hz,1H),14.76(s,1H)。
Synthesis of luminescent material p-tBuCz-BF 2: in a dry 50mL three-necked flask was added p-tBuCz-OH (230 mg,0.52mmol,1.0 eq.) and methylene chloride (15 mL), then boron trifluoride diethyl ether (0.2 mL,1.56mmol,3.0 eq.) was added at-15℃and the reaction was stirred at room temperature for 2 hours and then N, N-diisopropylethylamine (0.37 mL,2.09mmol,4.0 eq.) was added and the reaction continued for 12 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:2, giving 139mg of a yellowish green solid in 54% yield. 1 H NMR(500MHz,CDCl 3 )δ1.47(s,18H),7.33(dd,J＝8.5,2.0Hz,1H),7.46(d,J＝2.0Hz,1H),7.48(dd,J＝8.5,2.0Hz,2H),7.54(d,J＝8.5Hz,2H),7.61-7.64(m,1H),8.02(d,J＝8.5Hz,1H),8.13(d,J＝1.5Hz,2H),8.18(d,J＝8.5Hz,1H),8.22-8.25(m,1H),8.76(d,J＝5.5Hz,1H)。
Example 4: the luminescent material p-PTZ-BF2 may be synthesized as follows:
synthesis of intermediate p-PTZ-OH: 2-Br (400 mg,1.60mmol,1.0 eq), phenothiazine (415 mg,2.08mmol,1.3 eq), sodium tert-butoxide (463mg, 4.8mmol,3.0 eq) and palladium acetate (11 mg,0.048mmol,0.03 eq) were successively added to a 50mL three-port flask, then nitrogen was purged three times, and tri-tert-butylphosphine (260 mg,0.13mmol,0.08 eq, 10wt% toluene) and 1,4 dioxane (15 mL) were added by injection and reacted at 100℃in an oil bath for 50 hours. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/ethyl acetate=50:1-10:1, giving 435mg as a tan solid in 74% yield. 1 H NMR(500MHz,CDCl 3 )δ6.70(dd,J＝8.0,1.5Hz,2H),6.83(dd,J＝8.5,2.5Hz,1H),6.92(td,J＝7.5,1.5Hz,2H),6.97–7.01(m,3H),7.13(dd,J＝7.5,1.5Hz,2H),7.26–7.29(m,1H),7.84–7.92(m,3H),8.53(ddd,J＝5.0,2.0,1.0Hz,1H),14.63(s,1H)。
Synthesis of luminescent material p-PTZ-BF 2: in a dry 50mL three-necked flask, p-PTZ-OH (400 mg,1.09mmol,1.0 eq.) and methylene chloride (10 mL) were added, then boron trifluoride diethyl ether (0.4 mL,3.26mmol,3.0 eq.) was added at-15℃and the reaction was stirred at room temperature for 3 hours, then N, N-diisopropylethylamine (0.76 mL,4.36mmol,4.0 eq.) was added and the reaction continued for 17 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:1, giving 260mg of orange solid in 57% yield. 1 H NMR(500MHz,CDCl 3 )δ6.13(dd,J＝8.0,1.5Hz,2H),6.63(td,J＝7.5,1.5Hz,2H),6.69(td,J＝7.5,1.5Hz,2H),6.72(dd,J＝7.5,1.5Hz,2H),7.06(dd,J＝8.5,2.0Hz,1H),7.23(d,J＝2.0Hz,1H),7.67(ddd,J＝7.5,6.0,1.0Hz,1H),8.06(d,J＝8.5Hz,1H),8.18(d,J＝8.5Hz,1H),8.26(ddd,J＝9.0,7.5,1.5Hz,1H),8.78(d,J＝6.0Hz,1H)。
Example 5: the luminescent material p-PXZ-BF2 can be synthesized as follows:
synthesis of intermediate p-PXZ-OH: 2-Br (400 mg,1.60mmol,1.0 eq), phenoxazine (383mg, 2.08mmol,1.3 eq), sodium tert-butoxide (463mg, 4.8mmol,3.0 eq) and palladium acetate (11 mg,0.048mmol,0.03 eq) were successively added to a 50mL three-port flask, then nitrogen was purged three times, and tri-tert-butylphosphine (260 mg,0.13mmol,0.08 eq, 10wt% toluene) and 1,4 dioxane (15 mL) were added by injection and reacted at 100℃in an oil bath for 50 hours. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/ethyl acetate=50:1-10:1, resulting in 570mg of yellow solid in 88% yield. 1 H NMR(500MHz,CDCl 3 )δ6.13(dd,J＝8.0,1.5Hz,2H),6.63(ddd,J＝8.0,7.0,1.5Hz,2H),6.69(td,J＝7.5,1.5Hz,2H),6.73(dd,J＝7.5,1.5Hz,2H),7.06(dd,J＝8.5,2.0Hz,1H),7.23(d,J＝2.0Hz,1H),7.67(ddd,J＝7.5,6.0,1.0Hz,1H),8.06(d,J＝8.5Hz,1H),8.18(d,J＝8.5Hz,1H),8.26(ddd,J＝9.0,7.5,1.5Hz,1H),8.78(d,J＝6.0Hz,1H)。
Synthesis of luminescent material p-PXZ-BF 2: in a dry 50mL three-necked flask, p-PXZ-OH (570 mg,1.62mmol,1.0 eq.) and methylene chloride (12 mL) were added, then boron trifluoride diethyl ether (0.6 mL,4.85mmol,3.0 eq.) was added at-15℃and the reaction was stirred at room temperature for 2 hours, then N, N-diisopropylethylamine (0.1 mL,6.48mmol,4.0 eq.) was added and the reaction was continued for 17 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:1, giving orange solid 222mg, yield 39%. 1 H NMR(500MHz,CDCl 3 )δ6.71(dd,J＝9.0,2.5Hz,1H),6.84(d,J＝2.5Hz,1H),7.18(td,J＝7.5,1.5Hz,2H),7.30(td,J＝7.5,1.5Hz,2H),7.36(dd,J＝8.0,1.5Hz,2H),7.40–7.43(m,3H),7.64(d,J＝9.0Hz,1H),7.91(d,J＝8.5Hz,1H),8.05(ddd,J＝8.5,7.5,1.5Hz,1H),8.57(d,J＝6.0Hz,1H)。
Example 6: the luminescent material p-DMAC-BF2 may be synthesized as follows:
synthesis of intermediate p-DMAC-OMe: 1-Br (1.0 g,3.79mmol,1.0 eq.) acridine (951 mg,4.54mmol,1.2 eq.) sodium tert-butoxide (428 mg,7.58mmol,2.0 eq.) Pd was added sequentially to a 50mL three-necked flask 2 (dba) 3 (104 mg,0.11mmol,0.03 eq.) and S-Phos (93 mg,0.23mmol,0.06 eq.) were then purged with nitrogen three times and toluene (15 mL) was added by injection and reacted at 110℃for 67 hours in an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/ethyl acetate=50:1-10:1, giving 1.35g of a tan solid with 91% yield. 1 H NMR(500MHz,CDCl 3 )δ1.72(s,6H),3.83(s,3H),6.42(dd,J＝8.0,1.5Hz,2H),6.93–6.96(m,3H),7.00(ddd,J＝8.5,7.0,1.5Hz,2H),7.08(dd,J＝8.0,1.5Hz,1H),7.26–7.29(m,1H),7.47(dd,J＝7.5,1.5Hz,2H),7.78(td,J＝7.5,2.0Hz,1H),7.92(dt,J＝8.0,1.0Hz,1H),8.02(d,J＝8.0Hz,1H),8.76(ddd,J＝5.0,2.0,1.0Hz,1H)。
Synthesis of intermediate p-DMAC-OH: to a dry 50mL three-necked flask was added p-DMAC-OMe (1.18 g,3.0mmol,1.0 eq.) and dried dichloromethane (20 mL). Boron tribromide (0.85 mL,9.0mmol,3.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 19 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting with: petroleum ether/ethyl acetate=20:1-11, 760mg of yellow solid was obtained in 67% yield. 1 H NMR(500MHz,CDCl 3 )δ1.69(s,6H),6.48(dd,J＝8.0,1.5Hz,2H),6.88(dd,J＝8.5,2.0Hz,1H),6.93(td,J＝7.5,1.5Hz,2H),6.97–7.01(m,2H),7.05(d,J＝2.0Hz,1H),7.32(ddd,J＝7.5,5.0,1.0Hz,1H),7.46(dd,J＝7.5,1.5Hz,2H),7.91(td,J＝8.0,2.0Hz,1H),7.98–8.01(m,1H),8.04(d,J＝8.5Hz,1H),8.58(ddd,J＝5.0,2.0,1.0Hz,1H),14.67(s,1H)。
Synthesis of luminescent material p-DMAC-BF 2: in a dry 50mL three-necked flask, p-DMAC-OH (620 mg,1.64mmol,1.0 eq.) and methylene chloride (10 mL) were added, then boron trifluoride diethyl ether (2.07 mL,10.4mmol,10 eq.) was added at-15℃and the reaction was stirred at room temperature for 3 hours, then N, N-diisopropylethylamine (4.3 mL,24.6mmol,15 eq.) was added and the reaction was continued for 42 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:1, resulting in 570mg of yellow solid with a yield of 82%. 1 H NMR(400MHz,CDCl 3 )δ1.67(s,6H),6.55(d,J＝7.6Hz,2H),6.96–7.05(m,5H),7.24(s,1H),7.47(d,J＝7.2Hz,2H),7.64(t,J＝6.4Hz,1H),8.05(d,J＝8.4Hz,1H),8.18(d,J＝8.4Hz,1H),8.24(t,J＝8.0Hz,1H),8.76(d,J＝6.0Hz,1H)。
Example 7: the luminescent material p-DPA-BF2 can be synthesized as follows:
synthesis of intermediate p-DPA-OMe: 1-Br (788 mg,2.98mmol,1.0 eq.) diphenylamine (606 mg,3.58mmol,1.2 eq.) sodium t-butoxide (573 mg,5.96mmol,2.0 eq.) Pd was added sequentially to a 50mL three-necked flask 2 (dba) 3 (82 mg,0.09mmol,0.03 eq.) and S-Phos (73 mg,0.18mmol,0.06 eq.) were then purged with nitrogen three times and toluene (12 mL) was added by injection and reacted at 110℃for 96 hours in an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the organic phases combined, dried over anhydrous sodium sulfate, filtered and subtractedThe solvent is removed by pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent is as follows: petroleum ether/ethyl acetate=50:1-10:1, giving 975mg of a tan solid in 93% yield. 1 H NMR(400MHz,CDCl 3 )δ3.70(s,3H),6.68(s,1H),6.74(d,J＝8.8Hz,1H),7.07(t,J＝7.2Hz,2H),7.16(d,J＝8.0Hz,4H),7.21(d,J＝6.4Hz,1H),7.26–7.31(m,4H),7.69(d,J＝8.4Hz,1H),7.76(t,J＝8.0Hz,1H),7.86(d,J＝8.0Hz,1H),8.72(d,J＝4.8Hz,1H)。
Synthesis of intermediate p-DPA-OH: to a dry 50mL three-necked flask was added p-DPA-OMe (925 mg,2.62mmol,1.0 eq.) and dried dichloromethane (30 mL). Boron tribromide (0.74 mL,7.87mmol,3.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 26 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting with: petroleum ether/ethyl acetate=20:1-1:1, giving 297mg of a white solid in 33% yield. 1 H NMR(400MHz,CDCl 3 )δ6.57(dd,J＝8.4,2.4Hz,1H),6.69(s,1H),7.09(t,J＝7.2Hz,2H),7.15–7.22(m,5H),7.27–7.31(m,4H),7.60(d,J＝8.4Hz,1H),7.79–7.86(m,2H),8.46(d,J＝4.8Hz,1H),14.40(s,1H)。
Synthesis of luminescent material p-DPA-BF 2: in a dry 50mL three-necked flask, p-DPA-OH (250 mg,0.74mmol,1.0 eq.) and methylene chloride (10 mL) were added, then boron trifluoride diethyl ether (0.93 mL,7.39mmol,10 eq.) was added at-15℃and the reaction was stirred at room temperature for 1.5 hours, then N, N-diisopropylethylamine (1.94 mL,11.1mmol,15 eq.) was added and the reaction was continued for 26 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:1, giving 245mg of yellow solid in 86% yield. 1 H NMR(400MHz,CDCl 3 )δ6.62–6.66(m,2H),7.14–7.20(m,6H),7.31–7.35(m,4H),7.39(t,J＝6.8Hz,1H),7.59(d,J＝8.8Hz,1H),7.91(d,J＝8.8Hz,1H),8.04(t,J＝8.0Hz,1H),8.56(d,J＝6.0Hz,1H)。
Example 8: the luminescent material m-Cz-BF2 may be synthesized as follows:
synthesis of intermediate 1-Cl: in a 250mL three-necked flask, 2-bromopyridine (13.53 g,85.84mmol,2.0 eq), 5-chloro-2-methoxyphenylboronic acid (8.0 g,42.92mmol,1.0 eq), cesium carbonate (34.96 g,107.3mmol,2.5 eq) and tetrakis triphenylphosphine palladium (992 mg,0.86mmol,0.02 eq) were sequentially added, followed by three nitrogen injections, ethanol (120 mL) and water (50 mL) were added and reacted at 80℃for 96 hours under an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/ethyl acetate=50:1-10:1, giving 7.07g of colorless liquid with 75% yield. 1 H NMR(500MHz,CDCl 3 )δ3.86(s,3H),6.94(d,J＝8.5Hz,1H),7.27–7.29(m,1H),7.33(dd,J＝8.5,2.5Hz,1H),7.75–7.78(m,2H),7.83(dt,J＝7.5,1.0Hz,1H),8.73(d,J＝4.5Hz,1H)。
Synthesis of intermediate m-Cz-OMe: 1-Cl (2.0 g,9.10mmol,1.0 eq), carbazole (1.83 g,10.93mmol,1.2 eq.), sodium tert-butoxide (2.19 g,22.75mmol,2.5 eq.) and Pd were added sequentially in a 100mL three-necked flask 2 (dba) 3 (250 mg,0.27mmol,0.03 eq.) and XPhos (260 mg,0.55mmol,0.06 eq.) then nitrogen was purged three times and o-xylene (30 mL) was added by injection and reacted at 140℃for 50 hours in an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/dichloromethane=30:1-1:1, giving 2.93g of brown solid in 92% yield. 1 H NMR(500MHz,CDCl 3 )δ4.01(s,3H),7.23–7.26(m,1H),7.26–7.34(m,3H),7.38–7.42(m,4H),7.57(dd,J＝9.0,2.5Hz,1H),7.84(t,J＝7.5Hz,1H),7.93(d,J＝8.0Hz,1H),7.96(d,J＝2.5Hz,1H),8.14(dt,J＝7.5,1.0Hz,2H),8.73(d,J＝2.0Hz,1H)。
Synthesis of intermediate m-Cz-OH: into a dry 500mL three-necked flask was addedm-Cz-OMe (2.94 g,8.39mmol,1.0 eq.) was added, dried dichloromethane (150 mL). Boron tribromide (1.59 mL,16.78mmol,2.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 18 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting with: petroleum ether/ethyl acetate=20:1-10:1, yielding 2.25g of yellow solid with 80% yield. 1 H NMR(500MHz,CDCl 3 )δ7.27–7.37(m,5H),7.40–7.44(m,3H),7.47(dd,J＝8.5,2.5Hz,1H),7.83–7.86(m,2H),7.94(d,J＝2.5Hz,1H),8.17(d,J＝7.5Hz,2H),8.61(d,J＝5.0Hz,1H),14.39(s,1H)。
Synthesis of luminescent material m-Cz-BF 2: in a dry 250mL three-necked flask, m-Cz-OH (2.25 g,6.69mmol,1.0 eq.) and methylene chloride (100 mL) were added, then boron trifluoride diethyl ether (2.53 mL,20.07mmol,3.0 eq.) was added at-15℃and the reaction was stirred at room temperature for 9 hours, then N, N-diisopropylethylamine (4.67 mL,26.76mmol,4.0 eq.) was added and the reaction was continued for 28 hours. After the reaction, the mixture is quenched by sodium carbonate solution, extracted by methylene chloride for three times, the organic phases are combined, dried by anhydrous sodium sulfate, filtered, the solvent is removed by reduced pressure distillation, the crude product is separated by silica gel column chromatography, and the leaching agent: petroleum ether/dichloromethane=5:1-1:1, giving 970mg of yellow solid with a yield of 38%. 1 H NMR(500MHz,CDCl 3 )δ7.30–7.35(m,4H),7.41–7.45(m,3H),7.66–7.69(m,2H),8.02(d,J＝2.5Hz,1H),8.07(d,J＝8.5Hz,1H),8.17(dt,J＝7.5,1.0Hz,2H),8.21(ddd,J＝9.0,7.5,1.5Hz,1H),8.81(dd,J＝6.0,1.5Hz,1H)。
Example 9: the luminescent material m-PhCz-BF2 can be synthesized as follows:
synthesis of intermediate m-PhCz-OMe: 1-Cl (2.0 g,9.10mmol,1.0 eq), phenylcarbazole (3.49 g,10.93mmol,1.2 eq.), sodium tert-butoxide (2.19 g,22.75mmol,2.5 eq.) and Pd were added sequentially in a 100mL three-necked flask 2 (dba) 3 (250 mg,0.27mmol,0.03 eq)) And XPhos (260 mg,0.55mmol,0.06 eq.) followed by three nitrogen injections and o-xylene (30 mL) were added and reacted for 48 hours at 140℃in an oil bath. The reaction was cooled to room temperature, quenched with water, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography on silica gel, and the eluent: petroleum ether/dichloromethane=5:1-1:100, giving 2.98g of brown solid in 65% yield. 1 H NMR(500MHz,CDCl 3 )δ4.03(s,3H),7.27(d,J＝9.0Hz,1H),7.33–7.37(m,3H),7.47–7.51(m,6H),7.64(dd,J＝8.5,3.0Hz,1H),7.68(dd,J＝8.5,2.0Hz,2H),7.72–7.75(m,4H),7.89–7.90(m,1H),7.96(d,J＝8.0Hz,1H),8.01(d,J＝2.5Hz,1H),8.40(d,J＝2.0Hz,2H),8.78(d,J＝2.0Hz,1H)。
Synthesis of intermediate m-PhCz-OH: in a dry 500mL three-necked flask was added m-PhCz-OMe (2.98 g,5.93mmol,1.0 eq.) and dried dichloromethane (150 mL). Boron tribromide (1.12 mL,11.86mmol,2.0 eq.) was then added dropwise at-15℃and the reaction was stirred at room temperature for 18 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting with: petroleum ether/dichloromethane=20:1-1:1, yielding 2.48g of yellow solid in 86% yield. 1 H NMR(500MHz,DMSO-d 6 )δ7.25(d,J＝8.7Hz,1H),7.34–7.38(m,2H),7.43(d,J＝8.5Hz,2H),7.49–7.53(m,5H),7.58(dd,J＝8.5,2.5Hz,1H),7.79(dd,J＝8.5,2.0Hz,2H),7.81–7.84(m,4H),8.02(td,J＝8.5,2.0Hz,1H),8.34–8.36(m,2H),8.70–8.72(m,1H),8.74(d,J＝2.0Hz,2H),14.49(s,1H)。
Synthesis of luminescent material m-PhCz-BF 2: in a dry 250mL three-necked flask, m-PhCz-OH (2.28 g,4.67mmol,1.0 eq.) and methylene chloride (50 mL) were added, then boron trifluoride diethyl ether (5.89 mL,46.67mmol,10 eq.) was added at-15℃and the reaction was stirred at room temperature for 9 hours, then N, N-diisopropylethylamine (12.26 mL,70.05mmol,15 eq.) was added and the reaction was continued for 28 hours. Quenching with sodium carbonate solution after the reaction, extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography,eluent: petroleum ether/dichloromethane=20:1-1:1, yielding 1.70g of yellow solid with a yield of 68%. 1 H NMR(500MHz,CDCl 3 )δ7.35–7.39(m,2H),7.42(dd,J＝8.5,1.0Hz,2H),7.47–7.51(m,5H),7.68–7.71(m,3H),7.73–7.75(m,5H),8.07(d,J＝2.5Hz,1H),8.11(d,J＝8.5Hz,1H),8.23(ddd,J＝9.0,7.5,1.5Hz,1H),8.43(dd,J＝1.8,0.5Hz,2H),8.83(d,J＝6.0Hz,1H)。
Performance evaluation examples
The complexes prepared in the above examples of the invention were subjected to photophysical, electrochemical and thermogravimetric analysis as follows:
photophysical analysis: phosphorescent emission spectrum, fluorescent emission spectrum, triplet state lifetime and excited state lifetime were all tested on a HORIBA FL3-11 spectrometer. Test conditions: in the low temperature and room temperature emission spectra, all samples were toluene (chromatographic grade) dilute solutions (10 -5 -10 -6 M) is selected from the group consisting of; both the luminescence quantum efficiency (PLQY) and luminescence decay curves were measured for 10wt% luminescent material doped DEPEO film samples.
FIG. 1 is the emission spectra of toluene solutions of the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2, respectively, at room temperature.
FIG. 2 is an emission spectrum of DEPEO films of luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 at room temperature.
FIG. 3 is a plot of DEPEO film luminescence decay (normalized luminescence intensity versus time) for luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2, and m-PhCz-BF 2.
TABLE 1 photophysical Properties of luminescent materials
Luminescent materialMaterial Peak/nm PLQY/％
p-Cz-BF2 438 99
p-tBuCz-BF2 459 99
p-PhCz-BF2 455 99
p-DPA-BF2 474 93
p-PXZ-BF2 565 24
p-PTZ-BF2 457、583 36
p-DMAC-BF2 528 78
m-Cz-BF2 487 99
m-PhCz-BF2 491 99
Note that: peak refers to the strongest emission Peak of the emission spectrum of a luminescent material in toluene solution at room temperature. PLQY refers to the absolute luminescence quantum efficiency of a 10wt% luminescent material doped DEPEO film sample.
As can be seen from fig. 1, fig. 2 and table 1: firstly, the luminous color of the material is easy to adjust: under the condition of keeping the acceptor structure unchanged, the luminous color of the material can cover the whole visible light region from blue light to orange light by simply adjusting the structure of the donor; secondly, the quantum efficiency of the material is high: the material has very high luminous quantum efficiency (PLQY), especially blue light material up to 99%. Thirdly, thermally-induced delayed fluorescent material: as can be seen from the luminescence decay (normalized luminescence intensity-time) curve of the DEPEO film of the material of FIG. 3, most of the DEPEO film is in a double-exponential decay mode, and is a typical thermally-induced delayed fluorescent material, the quantum efficiency of 100% can be achieved by fully utilizing excitons in a triplet state through reverse intersystem crossing in theory. These properties are all advantageous for their application as doped emitters in OLED devices and provide an effective way to address the current shortfall of blue light emitting materials, greatly promoting the development of this field.
Device instance
All materials were subjected to high vacuum (10 -5 -10 -6 Torr) was purified by gradient heating sublimation. Indium Tin Oxide (ITO) substrates used in the devices were all subjected to sequential ultrasonic treatment in deionized water, acetone, and isopropyl alcohol. The device is manufactured by vacuum degree of less than 10 -7 Vacuum thermal evaporation under the pressure of Torr. The anode electrode has a thickness ofIndium Tin Oxide (ITO) with a cathode consisting of a thickness +.>Li of (2) 2 CO 3 And->Al composition of (c). After all devices were prepared, the glass cover and epoxy resin were encapsulated in a nitrogen glove box and moisture absorbent was added to the package.
The device structures of the luminescent materials p-Cz-BF2 and m-PhCz-BF2 as luminophores under different host materials and transport materials are as follows:
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:1,5％,30nm)/PPT(2nm)/Bepp2:Li 2 CO 3 (5％,35nm)/Li 2 CO 3 (1 nm)/Al, device 1;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:2,5％,30nm)/PPT(2nm)/Bepp2:Li 2 CO 3 (5％,35nm)/Li 2 CO 3 (1 nm)/Al, device 2;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:1,5％,30nm)/PPT(2nm)/PPT:Li 2 CO 3 (5％,35nm)/Li 2 CO 3 (1 nm)/Al, device 3;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:2,5％,30nm)/PPT(2nm)/PPT:Li 2 CO 3 (5％,35nm)/Li 2 CO 3 (1 nm)/Al, device 4;
ITO/HATCN(10nm)/NPB(40nm)/mCBP(10nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li 2 CO 3 (5％,30nm)/Li 2 CO 3 (1 nm)/Al, device 5;
ITO/HATCN(10nm)/NPB(50nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li 2 CO 3 (5％,30nm)/Li 2 CO 3 (1 nm)/Al, device 6;
ITO/HATCN(10nm)/NPB(40nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li 2 CO 3 (5％,30nm)/Li 2 CO 3 (1 nm)/Al, device 7;
ITO/HATCN(15nm)/NPB(50nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li 2 CO 3 (5％,30nm)/Li 2 CO 3 (1 nm)/Al, device 8;
the molecular structure of the materials used in the device is as follows:
FIG. 4 is an electroluminescent spectrum of a device with a luminescent material p-Cz-BF2 as a light emitter doped differently in different proportions of the dual host material and with electron transport materials.
Fig. 5 is a graph of current density vs. voltage vs. luminous intensity for a device with a different proportion of a bi-host material and a different doping of an electron transport material with a luminescent material p-Cz-BF2 as a light emitter.
Fig. 6 is a graph of external quantum efficiency versus current density for a device with different proportions of the dual host material and different doping of the electron transport material with the luminescent material p-Cz-BF2 as the emitter.
FIG. 7 is an electroluminescent spectrum of a device with a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
Fig. 8 is a plot of device current density versus voltage versus luminous intensity for a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
Fig. 9 is a graph of external quantum efficiency versus current density for a device with a luminescent material m-PhCz-BF2 as a light emitter at different functional layer thicknesses.
As can be seen from fig. 8 and 9, the luminescent material m-PhCz-BF2 is used as the luminescent material, which has good device performance under different devices, and the maximum external quantum efficiency of the devices 5, 6, 7 and 8 is up to 23.9%, 25.6%, 22.4% and 10.2%, respectively; the maximum luminous brightness of the devices 5, 6, 7, 8 is up to 17493, 12633, 14029 and 13250cd/m respectively 2 . The device data fully show that the organic luminescent material containing the phenoxy-pyridine chelate boron difluoride acceptor is feasible as a luminescent material, the excellent performance of the organic luminescent material can be used as a thermally-induced delayed fluorescent material, and the organic luminescent material has great application prospect in the OLED field and promotes the further development of the field.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of carrying out the invention and that various changes in form and details may be made therein without departing from the spirit and scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention.

Claims (3)

1. An organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor is characterized in that: the thermal activation delay fluorescent material is a compound shown in a formula (1):
wherein,
in the formula (1), R a3 、R b3 Each independently is hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 An aryloxy group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m 3 、n 3 r is respectively a3 And R is b3 Is the number of (3); wherein m is 3 Is an integer of 0 to 4, n 3 An integer of 0 to 3;
said donor D 3 Is one of the following structures:
wherein,
R 1 '、R 2 '、R 3 '、R 4 '、R 7 '、R 8 '、R 10 '、R 11 '、R 12 '、R 13 '、R 14 ' and R 15 ' each independently hydrogen, deuterium, C 1 -C 24 Alkyl, C of (2) 1 -C 24 Alkoxy, C 3 -C 24 Cycloalkyl, C 1 -C 24 Ethers, C 1 -C 24 Heterocyclic groups of C 4 -C 24 Aryl, C of (2) 4 -C 24 Aryloxy, halogen, silicon-based, mono-or di-alkylamino, mono-or di-arylamino, cyano, or combinations thereof, wherein two adjacent substituents may be fused to form a ring;
o 2 、p 2 、q 2 、r 2 、s 2 、t 2 、u 2 、v 2 、w 2 、x 2 、y 2 and z 2 R is respectively 1’ 、R 2’ 、R 3’ 、R 4’ 、R 7’ 、R 8’ 、R 10’ 、R 11’ 、R 12’ 、R 13’ 、R 14’ And R is 15’ Is the number of (3);
o 2 and p 2 Is an integer of 0 to 5; q 2 、r 2 、s 2 、t 2 、u 2 、v 2 、w 2 、x 2 、y 2 And z 2 Is an integer of 0 to 4.
2. The thermally activated delayed fluorescence material of claim 1, wherein: the thermal activation delay fluorescent material is one of the following:
。
3. an organic electroluminescent device, characterized in that at least one of a light-emitting material, a host material, and other functional layer materials in the organic electroluminescent device comprises the thermally activated delayed fluorescence material according to any one of claims 1 to 2.
CN202210204059.7A 2022-03-02 2022-03-02 Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof Active CN114560880B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210204059.7A CN114560880B (en) 2022-03-02 2022-03-02 Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210204059.7A CN114560880B (en) 2022-03-02 2022-03-02 Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof

Publications (2)

Publication Number Publication Date
CN114560880A CN114560880A (en) 2022-05-31
CN114560880B true CN114560880B (en) 2024-01-26

Family

ID=81718595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210204059.7A Active CN114560880B (en) 2022-03-02 2022-03-02 Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof

Country Status (1)

Country Link
CN (1) CN114560880B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003257A (en) * 2019-04-23 2019-07-12 浙江虹舞科技有限公司 One kind contains bifluoride nitrogen-boron-oxygen heterocyclic receptor structural unit luminous organic material and its application
CN113234098A (en) * 2021-05-19 2021-08-10 浙江虹舞科技有限公司 Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003257A (en) * 2019-04-23 2019-07-12 浙江虹舞科技有限公司 One kind contains bifluoride nitrogen-boron-oxygen heterocyclic receptor structural unit luminous organic material and its application
CN113234098A (en) * 2021-05-19 2021-08-10 浙江虹舞科技有限公司 Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C-H activation based Copper-Catalyzed One-Shot Synthesis of N,O-Bidentate Organic Difluoroboron Complexes;Tan, Guangying et al.;Angewandte Chemie, International Edition;第59卷(第48期);21541-21545 *

Also Published As

Publication number Publication date
CN114560880A (en) 2022-05-31

Similar Documents

Publication Publication Date Title
CN108586507B (en) Long-life boron-containing organic electroluminescent compound and application thereof
CN107021926B (en) Compound containing azaspirofluorene and nitrogen-containing six-membered heterocycle and application of compound in OLED
CN112645968B (en) Fused ring compound containing two boron atoms and two oxygen family atoms and organic electroluminescent device
CN110627822A (en) Green light narrow spectrum three-coordination boron luminescent compound, luminescent composition and application thereof
CN107556297B (en) Xanthene organic compound and application thereof
CN109824684B (en) Spirofluorene derivative organic compound and application thereof in organic electroluminescent device
CN112961148B (en) Pyrazine receptor-based organic thermally-induced delayed fluorescent material and preparation method and application thereof
CN107513034B (en) Dimethyl anthracene organic compound and application thereof
KR20140138393A (en) Asymmetric ortho-Terphenyl Derivatives and Organic light emitting device Comprising the Same
CN111825618B (en) Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof
JP2024518728A (en) High emissivity platinum complexes with 1,8-substituted carbazoles and uses thereof
CN107522705B (en) Xanthene organic compound and application thereof in OLED
WO2021000434A1 (en) Red, green and blue thermally activated delayed fluorescent material, synthesis method therefor and use thereof
CN109575058B (en) 4, 10-dioxo-5, 9-diboropyrene derivative, preparation method and application
CN110294735B (en) Compound with anthracene and phenanthrene as core and application of compound in organic electroluminescent device
CN107686487B (en) Dimethyl anthracene organic compound and application thereof in organic electroluminescent device
CN114249759A (en) Bora Z-type acene derivative and preparation method and application thereof
CN110003257B (en) Organic luminescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor structural unit and application thereof
CN109574908B (en) Compound containing spirodimethyl anthracene fluorene and application thereof in organic electroluminescent device
CN107226811B (en) Organic compound with bigeminal dibenzo five-membered heterocyclic ring as framework and application of organic compound in OLED
CN114560880B (en) Organic thermal activation delay fluorescent material constructed by phenol oxygen-pyridine chelate boron difluoride receptor and application thereof
CN113620947B (en) Anthracene derivative and preparation method and application thereof
CN112174959B (en) Organic luminescent material based on 1,6-naphthyridine receptor structural unit and application thereof
CN108774236A (en) A kind of heterocyclic compound and its organic electroluminescence device
CN110551112A (en) Dicyano pyrazine-containing compound and application thereof in organic electroluminescent device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant