CN109897065A - Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus - Google Patents
Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus Download PDFInfo
- Publication number
- CN109897065A CN109897065A CN201910305989.XA CN201910305989A CN109897065A CN 109897065 A CN109897065 A CN 109897065A CN 201910305989 A CN201910305989 A CN 201910305989A CN 109897065 A CN109897065 A CN 109897065A
- Authority
- CN
- China
- Prior art keywords
- thermal activation
- delayed fluorescence
- layer
- activation delayed
- compound
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 89
- 230000003111 delayed effect Effects 0.000 title claims abstract description 29
- 238000007725 thermal activation Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000003636 chemical group Chemical group 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical group C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 8
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 8
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 8
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 8
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 tri-tert-butylphosphine tetrafluoroborate Chemical compound 0.000 claims description 6
- HWTHOPMRUCFPBX-UHFFFAOYSA-N 9,9-diphenyl-10h-acridine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 HWTHOPMRUCFPBX-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical group O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000007445 Chromatographic isolation Methods 0.000 claims description 2
- 238000011097 chromatography purification Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 150000004696 coordination complex Chemical class 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003760 hair shine Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- KDOKHBNNNHBVNJ-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12.N1C=CC=CC=C1 Chemical class C1=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12.N1C=CC=CC=C1 KDOKHBNNNHBVNJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/64—Acridine or hydrogenated acridine ring 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus, the general structure of the thermal activation delayed fluorescence material is as shown in following formula one: formula oneR indicates the chemical group as electron donor.Thermal activation delayed fluorescence material of the invention has ultrafast reversed intersystem crossing rate and high-luminous-efficiency, for the blue light TADF material with significant TADF characteristic and high level, the present invention utilizes the interior quantum utilization efficiency of TADF material 100%, it is applied to organic electroluminescent diode apparatus using the thermal activation delayed fluorescence material as the material of main part of conventional fluorescent material, fluorescent device is enabled to reach the device efficiency to compare favourably with the phosphorescent devices of phosphorescence heavy metal complex, greatly improve exciton utilization rate, solving simultaneously directly uses TADF material as gamut differences caused by emitting layer material, the problems such as exciton lifetime is too long.
Description
Technical field
The invention belongs to electroluminescent material technical field, in particular to a kind of thermal activation delayed fluorescence material and its preparation
Method and organic electroluminescent diode apparatus.
Background technique
Organic electroluminescent LED (Organic Light-Emitting Diode, OLED) display panel is with its active
It shines and does not need that backlight, luminous efficiency are high, visible angle is big, fast response time, Acclimation temperature range are big, production and processing technology
Relatively easy, the advantages that driving voltage is low, energy consumption is small, lighter and thinner, Flexible Displays and huge application prospect, have attracted crowd
The concern of more researchers.
The principle of OLED device is, under electric field action, hole and electronics are injected from anode and cathode respectively, leads to respectively
Hole injection layer, hole transmission layer and electron injecting layer, electron transfer layer are crossed, is compounded to form exciton, exciton radiation in luminescent layer
Decaying shines.
Core component of the electroluminescent organic material as OLED device has the service performance of device very big
It influences.The emitting layer material of OLED device generally comprises the material of main part and guest materials of mixing, wherein the hair to play a leading role
Light guest materials is most important.The light emitting guest material that the OLED device of early stage uses is fluorescent material, since it is in OLED device
The exciton ratio of singlet state and triplet is 1:3, therefore the theoretical internal quantum efficiency of the OLED device based on fluorescent material in part
(IQE) it can only achieve 25%, significantly limit the application of fluorescence electroluminescent device.Heavy metal complex phosphor material due to
The Effect of Spin-orbit Coupling of heavy atom allows it to realize 100% using singlet state and triplet exciton simultaneously
IQE.However, usually used heavy metal is all the precious metals such as iridium (Ir), platinum (Pt), and heavy metal complex phosphorescence shines
Material still needs to be broken through in terms of blue light material.Pure organic thermal activation delayed fluorescence (TADF) material, have electron donor (D) and
The molecular structure that electron acceptor (A) combines, by cleverly MOLECULE DESIGN, so that molecule has lesser minimum three Beijing South Maxpower Technology Co. Ltd of list
Differential (Δ EST), such triplet exciton can return to singlet state by reversed intersystem crossing (RISC), then pass through radiation transistion
It shines to ground state, so as to which using single, triplet exciton, 100% IQE also may be implemented simultaneously.
For TADF material, quick reversed intersystem crossing constant (kRISC) and high photoluminescence quantum yield
It (PLQY) is the necessary condition for preparing high efficiency OLED device.Currently, having the TADF material of above-mentioned condition relative to heavy metal
It is still deficienter for Ir complex.And since TADF material has the exciton longevity of very wide spectrum and musec order
Life, significantly limits its application in volume production device architecture.
Summary of the invention
The purpose of the present invention is to provide a kind of thermal activation delayed fluorescence material, have ultrafast reversed intersystem crossing rate and
High-luminous-efficiency can be used as two pole of organic electroluminescent for the blue light TADF compound with significant TADF characteristic and high level
The luminescent layer material of main part of pipe.
Another object of the present invention is to provide a kind of preparation method of thermal activation delayed fluorescence material, and this method is easy to grasp
Make, and the yield for obtaining target product is higher.
Yet another object of that present invention is to a kind of organic electroluminescent diode apparatus is provided, using above-mentioned bipolarity thermal activation
Delayed fluorescence material can reach the device to compare favourably with the phosphorescent devices of phosphorescence heavy metal complex as luminescent layer material of main part
Part efficiency, while solving and directly using TADF material too long etc. as gamut differences caused by emitting layer material, exciton lifetime
Problem.
For achieving the above object, the present invention provides a kind of thermal activation delayed fluorescence material, has as shown in following formula one
Chemical structure:
Formula one
In above formula one, R indicates chemical group as electron donor, R is in the ortho position of phosphorus atoms in phenyl ring, align or
Meta position.
Any one of the chemical group R of the electron donor in following group:
The thermal activation delayed fluorescence material is compound 1, compound 2 or compound 3, the compound 1, compound 2
It is as follows with the structural formula difference of compound 3:
The present invention also provides a kind of preparation method of thermal activation delayed fluorescence material, chemical synthesis route is as follows:
Specifically: into reaction flask be added molar ratio be 1:1-2:0.02-0.1:0.1-0.2 halogenated raw material, contain electronics
Then donor compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate are 1- by with halogenated raw material under anhydrous and oxygen-free environment
Sodium tert-butoxide is added in the molar ratio of 2:1, and the toluene of water removal deoxygenation is squeezed under argon atmosphere, small in 110-130 DEG C of reaction 20-30
When；It is cooled to room temperature, reaction solution is poured into ice water, organic phase is merged after extraction, revolve into silica gel, column chromatographic isolation and purification obtains
Product, calculated yield；
The general structure of the halogenated raw material isWherein, Br is in phosphorus atoms in phenyl ring
Ortho position, contraposition or meta position；
The general structure containing electronic donor compound is R-H, wherein R indicates the chemical group as electron donor.
Any one of the chemical group R of the electron donor in following group:
The electronic donor compound that contains is 9,10- dihydro -9,9- diphenylacridine；
The halogenated raw material is raw material 1, raw material 2 or raw material 3, and the structural formula of the raw material 1, raw material 2 and raw material 3 is respectively
The present invention also provides a kind of organic electroluminescent diode apparatus, including substrate, be set on the substrate
One electrode, the organic function layer being set in first electrode and the second electrode being set on the organic function layer；
The organic function layer includes one or more layers organic film, and at least one layer of organic film is luminescent layer；
The luminescent layer includes mixed material of main part and guest materials, and it is living that the material of main part is selected from heat as described above
Change delayed fluorescence material.
The luminescent layer is formed using the method that vacuum evaporation or solution coat.
The guest materials is PPA.
The substrate is glass substrate, and the material of the first electrode is tin indium oxide, and the second electrode is lithium fluoride
The two-layer composite that layer is constituted with aluminium layer；
The organic function layer includes multilayer organic film, which includes hole injection layer, hole transport
Layer, luminescent layer, electron transfer layer, wherein the material of the hole injection layer is HATCN, and the material of the hole transmission layer is
TCTA, the material of the electron transfer layer are TmPyPB.
Compared to existing material and technology, the invention has the advantages that and the utility model has the advantages that
(1) thermal activation delayed fluorescence material of the invention has ultrafast reversed intersystem crossing rate and high-luminous-efficiency, is
Blue light TADF compound with significant TADF characteristic and high level, preparation method is easily operated, obtains the yield of target product
It is higher；
(2) organic electroluminescent diode apparatus of the invention, using the interior quantum utilization efficiency of TADF material 100%,
It is applied to organic electroluminescent LED using above-mentioned thermal activation delayed fluorescence material as the material of main part of conventional fluorescent material
Device enables fluorescent device to reach the device efficiency to compare favourably with the phosphorescent devices of phosphorescence heavy metal complex, greatly
Exciton utilization rate is improved, while solving and directly using TADF material as gamut differences caused by emitting layer material, exciton
The problems such as service life is too long, the organic electroluminescent diode apparatus based on thermal activation delayed fluorescence material of the invention all achieve
Very high device efficiency.
Detailed description of the invention
With reference to the accompanying drawing, by the way that detailed description of specific embodiments of the present invention, technical solution of the present invention will be made
And other beneficial effects are apparent.
In attached drawing,
The HOMO and lumo energy distribution map that Fig. 1 is compound 1-3 prepared in specific embodiment of the invention 1-3；
Fig. 2 is the photic hair in compound 1-3 prepared in specific embodiment of the invention 1-3 at room temperature toluene solution
Light spectrogram；
Fig. 3 is the structural schematic diagram of organic electroluminescent diode apparatus of the present invention.
Specific embodiment
The some raw materials being not specified used in the present invention are commercial goods.The preparation method of some compounds will be in reality
It applies in case and describes.The present invention is more specifically described in detail combined with specific embodiments below, but embodiment party of the invention
Formula is without being limited thereto.
Embodiment 1:
The synthetic route of target compound 1 is as follows:
Raw material 1 (2.68g, 5mmol) is added into bis- mouthfuls of bottles of 100mL, 9,10- dihydro -9,9- diphenylacridines (2.00g,
6mmol), palladium acetate Pb (OAc) (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (t-Bu)3HPBF4(0.17g,
0.6mmol), sodium tert-butoxide NaOt-Bu (0.58g, 6mmol) then is added in glove box, squeezes into 40mL under argon atmosphere
The toluene of water removal deoxygenation in advance, reacts 24 hours at 120 DEG C.It is cooled to room temperature, reaction solution is poured into 200mL ice water, dichloro
Methane extracts three times, merges organic phase, and rotation is isolated and purified, obtained at silica gel, column chromatography (methylene chloride: n-hexane, v:v, 3:1)
The compound 1 of 2.0g blue and white powder, yield 51%.
1HNMR(300MHz,CD2Cl2, δ): 7.73 (d, J=6.3Hz, 2H), 7.38 (d, J=6.9Hz, 2H), 7.26-
7.07(m,14H),6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.08.
Embodiment 2:
The synthetic route of target compound 2 is as follows:
Raw material 2 (2.68g, 5mmol) is added into bis- mouthfuls of bottles of 100mL, 9,10- dihydro -9,9- diphenylacridines (2.00g,
6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6mmol), then in glove box
Middle addition sodium tert-butoxide (0.58g, 6mmol), squeezes into the toluene that 40mL removes water deoxygenation in advance under argon atmosphere, anti-at 120 DEG C
It answers 24 hours.Be cooled to room temperature, reaction solution poured into 200mL ice water, methylene chloride extract three times, merge organic phase, rotation at
Silica gel, column chromatography (methylene chloride: n-hexane, v:v, 3:1) isolate and purify, and obtain the compound 2 of 1.6g blue and white powder, yield
41%.
1H NMR(300MHz,CD2Cl2,δ):7.57(s,1H),7.43-7.33(m,3H),7.26-7.07(m,14H),
6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.10.
Embodiment 3:
The synthetic route of target compound 3 is as follows:
Raw material 3 (2.68g, 5mmol) is added into bis- mouthfuls of bottles of 100mL, 9,10- dihydro -9,9- diphenylacridines (2.00g,
6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6mmol), then in glove box
Middle addition sodium tert-butoxide (0.58g, 6mmol), squeezes into the toluene that 40mL removes water deoxygenation in advance under argon atmosphere, anti-at 120 DEG C
It answers 24 hours.Be cooled to room temperature, reaction solution poured into 200mL ice water, methylene chloride extract three times, merge organic phase, rotation at
Silica gel, column chromatography (methylene chloride: n-hexane, v:v, 3:1) isolate and purify, and obtain the compound 3 of 1.0g blue and white powder, yield
25%.
1H NMR(300MHz,CD2Cl2, δ): 7.73 (d, J=6.9Hz, 1H), 7.54-7.38 (m, 2H), 7.32 (d, J=
6.3Hz,1H),7.26-7.07(m,14H),6.95-6.83(m,4H)。
MS(EI)m/z:[M]+calcd for C43H22F10NOP,789.13；found,789.11.
Fig. 1 shows the track arrangement situation of compound 1-3, it is apparent that the highest of compound 1-3 from Fig. 1
Electronics occupies track (HOMO) and do not occupy track (LUMO) from minimum electronics to be arranged on different units respectively, has been realized
Full separation, this facilitates the poor Δ EST of energy between reduction system, to improve reversed intersystem crossing ability.Fig. 2 shows compound 1-
3 photoluminescence spectras in toluene solution at room temperature.For compound 1-3, simulation calculates the minimum singlet energy of molecule
Grade S1 and lowest triplet state energy level T1.
The related data of embodiment 1-3 is as shown in table 1.As can be seen from Table 1, the Δ Est of all compounds is respectively less than
0.3ev, realizes lesser singlet and triplet is poor, has obvious delay fluorescent effect.
The photophysical property result of table 1, compound 1-3
In table 1, PL Peak indicates luminescence generated by light peak, and S1 indicates singlet energy level, and T1 indicates triplet, Δ EST table
Show that singlet and triplet are poor.
Embodiment 4:
The preparation of organic electroluminescent LED (OLED) device:
As described in Figure 1, the organic electroluminescent of thermal activation delayed fluorescence material of the invention as luminescent layer guest materials
Diode component, it may include the substrate 9 that sets gradually from top to bottom, hole injection layer 2, hole transmission layer 3, shines at anode layer 1
Layer 4, electron transfer layer 5 and cathode layer 6.Wherein, the substrate 9 is glass substrate, and the material of the anode 1 is tin indium oxide
(ITO), the substrate 9 collectively forms ito glass with anode 1.The material of the hole injection layer 2 is HATCN, and the hole passes
The material of defeated layer 3 is TCTA, and the material of the luminescent layer is the mixture of thermal activation delayed fluorescence material and PPA of the invention,
The material of the electron transfer layer 5 is TmPyPB, and the cathode is that the bilayer that lithium fluoride (LiF) layer and aluminium (Al) layer are constituted is tied
Structure.
Wherein, HATCN refers to that 2,3,6,7,10,11- six cyano-Isosorbide-5-Nitrae, 5,8,9,12- six azepine benzophenanthrenes, TCTA refer to 4,
4', 4 "-three (carbazole -9- base) triphenylamines, PPA refer to that 9- pyrenyl-(10) -4- triphenylamine base anthracene, TmPyPB refer to 1,3,5- tri- (3-
(3- pyridyl group) phenyl) benzene.
The organic electroluminescent diode apparatus can be made by means known in the art, method particularly includes: by clear
Successively be deposited on the ito glass washed, under high vacuum condition the HATCN film of 2nm thickness, the TCTA film of 35nm thickness, thermal activation delay it is glimmering
Luminescent material adds the Al film of the TmPyPB film of PPA, 40nm thickness, the LiF film of 1nm thickness and 100nm thickness.It is made with this method such as Fig. 3 institute
The device shown, various specific device architectures are as follows:
Device 1:
ITO/HATCN (2nm)/TCTA (35nm)/compound 1:PPA (20%40nm)/TmPyPB (40nm)/LiF
(1nm)/Al(100nm)
Device 2:
ITO/HATCN (2nm)/TCTA (35nm)/compound 2:PPA (20%40nm)/TmPyPB (40nm)/LiF
(1nm)/Al(100nm)
Device 3:
ITO/HATCN (2nm)/TCTA (35nm)/compound 3:PPA (20%40nm)/TmPyPB (40nm)/LiF
(1nm)/Al(100nm)
Current versus brightness-voltage characteristic of device 1-3 is surveyed by the source Keithley with corrected silicon photoelectric diode
What amount system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) was completed, electroluminescent light
Spectrum is by French JY company SPEX CCD3000 spectrometer measurement, and all measurements are completed in atmosphere at room temperature.Device 1-3's
Performance data see the table below 2.
Table 2, the results of property based on the device that compound 1-3 is luminescent layer material of main part
| Device | Maximum current efficiency (cd/A) | CIEy | Maximum external quantum efficiency (%) |
| Device 1 | 23.5 | 0.09 | 22.3% |
| Device 2 | 22.1 | 0.09 | 21.7% |
| Device 3 | 19.3 | 0.09 | 19.9% |
In table 2, CIEy is the y-coordinate value of standard CIE color space.
In conclusion the present invention by cleverly MOLECULE DESIGN, synthesized it is a series of have lower single triplet it is poor,
The thermal activation delayed fluorescence material of high-luminous-efficiency and snap back intersystem crossing constant is the height with significant TADF characteristic
The blue light TADF material of energy level, and synthetic route design is rationally, the yield for obtaining target product is higher, and the present invention further utilizes
The interior quantum utilization efficiency of TADF material 100%, using above-mentioned thermal activation delayed fluorescence material as the main body of conventional fluorescent material
Material and be applied to organic electroluminescent diode apparatus, enable fluorescent device to reach the phosphorus with phosphorescence heavy metal complex
The device efficiency that optical device compares favourably greatly improves exciton utilization rate, at the same solve directly use TADF material as
Gamut differences caused by emitting layer material, the problems such as exciton lifetime is too long.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of thermal activation delayed fluorescence material, which is characterized in that have the chemical structure as shown in following formula one:
Formula one
In above formula one, R indicates chemical group as electron donor, R is in the ortho position of phosphorus atoms in phenyl ring, align or
Position.
2. thermal activation delayed fluorescence material as described in claim 1, which is characterized in that the chemical group R of the electron donor
Any one in following group:
3. thermal activation delayed fluorescence material as claimed in claim 2, which is characterized in that be compound 1, compound 2 or chemical combination
The structural formula difference of object 3, the compound 1, compound 2 and compound 3 is as follows:
4. a kind of preparation method of thermal activation delayed fluorescence material, which is characterized in that its chemical synthesis route is as follows:
Specifically: into reaction flask be added molar ratio be 1:1-2:0.02-0.1:0.1-0.2 halogenated raw material, contain electron donor
Then compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate are 1-2:1's by with halogenated raw material under anhydrous and oxygen-free environment
Molar ratio be added sodium tert-butoxide, squeezed under argon atmosphere water removal deoxygenation toluene, 110-130 DEG C reaction 20-30 hours；It is cold
But to room temperature, reaction solution is poured into ice water, organic phase is merged after extraction, is revolved into silica gel, column chromatographic isolation and purification obtains product,
Calculated yield；
The general structure of the halogenated raw material isWherein, Br be in the ortho position of phosphorus atoms in phenyl ring,
Contraposition or meta position；
The general structure containing electronic donor compound is R-H, wherein R indicates the chemical group as electron donor.
5. the preparation method of thermal activation delayed fluorescence material as claimed in claim 4, which is characterized in that the electron donor
Any one of chemical group R in following group:
6. the preparation method of thermal activation delayed fluorescence material as claimed in claim 5, which is characterized in that described to contain electron donor
Compound is 9,10- dihydro -9,9- diphenylacridine；
The halogenated raw material is raw material 1, raw material 2 or raw material 3, and the structural formula of the raw material 1, raw material 2 and raw material 3 is respectively
7. a kind of organic electroluminescent diode apparatus, which is characterized in that including substrate, the first electricity being set on the substrate
Pole, the organic function layer being set in first electrode and the second electrode being set on the organic function layer；
The organic function layer includes one or more layers organic film, and at least one layer of organic film is luminescent layer；
The luminescent layer includes mixed material of main part and guest materials, and the material of main part is appointed in such as claim 1-3
Thermal activation delayed fluorescence material described in one.
8. organic electroluminescent diode apparatus as claimed in claim 7, which is characterized in that the luminescent layer is steamed using vacuum
The method of plating or solution coating is formed.
9. organic electroluminescent diode apparatus as claimed in claim 7, which is characterized in that the guest materials is PPA.
10. organic electroluminescent diode apparatus as claimed in claim 7, which is characterized in that the substrate is glass substrate,
The material of the first electrode is tin indium oxide, and the second electrode is the two-layer composite that layer of lithium fluoride and aluminium layer are constituted；
The organic function layer includes multilayer organic film, which includes hole injection layer, hole transmission layer, hair
Photosphere, electron transfer layer, wherein the material of the hole injection layer is HATCN, and the material of the hole transmission layer is TCTA,
The material of the electron transfer layer is TmPyPB.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910305989.XA CN109897065B (en) | 2019-04-16 | 2019-04-16 | Thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting diode device |
| PCT/CN2019/085646 WO2020211127A1 (en) | 2019-04-16 | 2019-05-06 | Thermally activated delayed fluorescence material and preparation method therefor, and organic light-emitting diode device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910305989.XA CN109897065B (en) | 2019-04-16 | 2019-04-16 | Thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting diode device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109897065A true CN109897065A (en) | 2019-06-18 |
| CN109897065B CN109897065B (en) | 2021-06-01 |
Family
ID=66955812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910305989.XA Active CN109897065B (en) | 2019-04-16 | 2019-04-16 | Thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting diode device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109897065B (en) |
| WO (1) | WO2020211127A1 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399244A (en) * | 2011-09-28 | 2012-04-04 | 昆山维信诺显示技术有限公司 | Dihydro acridine derivatives, application thereof and organic electroluminescent device applying same |
| CN107162974A (en) * | 2017-07-13 | 2017-09-15 | 长春海谱润斯科技有限公司 | A kind of acridine compounds and its organic luminescent device |
| CN108101941A (en) * | 2017-12-06 | 2018-06-01 | 深圳市华星光电技术有限公司 | Luminous organic material and its preparation method and application |
| CN108463898A (en) * | 2015-12-18 | 2018-08-28 | 诺瓦尔德股份有限公司 | Electron injecting layer for Organic Light Emitting Diode (OLED) |
| CN108658940A (en) * | 2018-07-18 | 2018-10-16 | 武汉华星光电半导体显示技术有限公司 | Thermal activation delayed fluorescence material, its synthetic method and OLED luminescent devices |
| CN108727429A (en) * | 2017-04-14 | 2018-11-02 | 三星显示有限公司 | Heterocyclic compound and organic luminescent device including the heterocyclic compound |
| CN108822018A (en) * | 2017-05-05 | 2018-11-16 | 吉林奥来德光电材料股份有限公司 | Electroluminescent organic material and preparation method thereof and organic electroluminescence device |
| CN109337676A (en) * | 2018-11-15 | 2019-02-15 | 武汉华星光电半导体显示技术有限公司 | A kind of dark blue photo-thermal activation delayed fluorescence material and its application |
| CN109503481A (en) * | 2018-12-17 | 2019-03-22 | 武汉华星光电半导体显示技术有限公司 | Thermal activation delayed fluorescence compound and preparation method thereof and organic electroluminescent diode apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11171294B2 (en) * | 2015-12-15 | 2021-11-09 | Merck Patent Gmbh | Esters containing aromatic groups as solvents for organic electronic formulations |
| CN106986894A (en) * | 2016-01-20 | 2017-07-28 | 中国科学院宁波材料技术与工程研究所 | Simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of sulphur, phosphorus heteroatoms substituted diphenylamine |
-
2019
- 2019-04-16 CN CN201910305989.XA patent/CN109897065B/en active Active
- 2019-05-06 WO PCT/CN2019/085646 patent/WO2020211127A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399244A (en) * | 2011-09-28 | 2012-04-04 | 昆山维信诺显示技术有限公司 | Dihydro acridine derivatives, application thereof and organic electroluminescent device applying same |
| CN108463898A (en) * | 2015-12-18 | 2018-08-28 | 诺瓦尔德股份有限公司 | Electron injecting layer for Organic Light Emitting Diode (OLED) |
| CN108727429A (en) * | 2017-04-14 | 2018-11-02 | 三星显示有限公司 | Heterocyclic compound and organic luminescent device including the heterocyclic compound |
| CN108822018A (en) * | 2017-05-05 | 2018-11-16 | 吉林奥来德光电材料股份有限公司 | Electroluminescent organic material and preparation method thereof and organic electroluminescence device |
| CN107162974A (en) * | 2017-07-13 | 2017-09-15 | 长春海谱润斯科技有限公司 | A kind of acridine compounds and its organic luminescent device |
| CN108101941A (en) * | 2017-12-06 | 2018-06-01 | 深圳市华星光电技术有限公司 | Luminous organic material and its preparation method and application |
| CN108658940A (en) * | 2018-07-18 | 2018-10-16 | 武汉华星光电半导体显示技术有限公司 | Thermal activation delayed fluorescence material, its synthetic method and OLED luminescent devices |
| CN109337676A (en) * | 2018-11-15 | 2019-02-15 | 武汉华星光电半导体显示技术有限公司 | A kind of dark blue photo-thermal activation delayed fluorescence material and its application |
| CN109503481A (en) * | 2018-12-17 | 2019-03-22 | 武汉华星光电半导体显示技术有限公司 | Thermal activation delayed fluorescence compound and preparation method thereof and organic electroluminescent diode apparatus |
Non-Patent Citations (1)
| Title |
|---|
| N. G. FROLOVA. ET AL: ""Addition of Bis(pentafluorophenyl)phosphinous Acid to Compounds with Activated C=C Bond as a Method for the Synthesis of First Tertiary P,P-Bis(pentafluorophenyl)phosphine Oxides"", 《DOKLADY CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020211127A1 (en) | 2020-10-22 |
| CN109897065B (en) | 2021-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102933531B (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| CN109970642A (en) | Bipolarity thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN110452182A (en) | A kind of host compound and the organic electroluminescence device using the compound | |
| WO2020124771A1 (en) | Thermally activated delayed fluorescent compound, preparation method therefor and organic electroluminescent diode device thereof | |
| WO2020238094A1 (en) | Efficient blue green-to-orange red light thermally activated delayed fluorescent material, preparation method therefor and use thereof | |
| CN110003194A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| US20200224089A1 (en) | Dark blue light thermally activated delayed fluorescence (tadf) material and application thereof | |
| CN110003222A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN109503508A (en) | Green light thermal activation delayed fluorescence material and its synthetic method, electroluminescent device | |
| CN109369652B (en) | Blue light thermal activation delayed fluorescent material and application thereof | |
| CN106632231B (en) | A kind of Hete rocyclic derivatives and the organic luminescent device using the Hete rocyclic derivatives | |
| WO2021000434A1 (en) | Red, green and blue thermally activated delayed fluorescent material, synthesis method therefor and use thereof | |
| US20200194682A1 (en) | Thermally activated delayed fluorescence material and method for preparing thereof and organic electroluminescent diode device | |
| CN110183426A (en) | A kind of thermal activation delayed fluorescence material, preparation method and electroluminescent device | |
| WO2020237885A1 (en) | Dark blue thermal activation delayed fluorescent material and preparation method therefor, and electroluminescent device | |
| CN108203420A (en) | Derivative of naphthalene benzofuran and anthracene and preparation method thereof, application and device | |
| CN110015994A (en) | Thermal activation delayed fluorescence material and preparation method thereof, display device | |
| CN109206368A (en) | A kind of dihydrobenzo indazole class electroluminescent organic material | |
| CN109206367A (en) | A kind of organic electroluminescence device and display | |
| CN110003223A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN109912505A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN110003208A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN109897065A (en) | Thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| WO2020124764A1 (en) | Red thermally activated delayed fluorescent material, preparation method therefor and organic light-emitting diode device | |
| US20200161578A1 (en) | Blue thermally activated delayed fluorescence material and application thereof |
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 |