CN109096252B - Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof - Google Patents
Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof Download PDFInfo
- Publication number
- CN109096252B CN109096252B CN201811148806.XA CN201811148806A CN109096252B CN 109096252 B CN109096252 B CN 109096252B CN 201811148806 A CN201811148806 A CN 201811148806A CN 109096252 B CN109096252 B CN 109096252B
- Authority
- CN
- China
- Prior art keywords
- donor
- biacridine
- acceptor
- derivative
- fluorescent material
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 55
- 230000003111 delayed effect Effects 0.000 title claims abstract description 19
- 230000000694 effects Effects 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 150000001251 acridines Chemical class 0.000 abstract description 3
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 150000001875 compounds Chemical class 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000000103 photoluminescence spectrum Methods 0.000 description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical class C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920001621 AMOLED Polymers 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VTSDGYDTWADUJQ-UHFFFAOYSA-N 2-bromoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 VTSDGYDTWADUJQ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SKQRTXKKLIPOGG-UHFFFAOYSA-N 1-acridin-1-ylacridine Chemical compound C1=CC=C2C=C3C(C4=CC=CC5=NC6=CC=CC=C6C=C54)=CC=CC3=NC2=C1 SKQRTXKKLIPOGG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- IIPRZFWOSCKSIM-UHFFFAOYSA-N 2,7,9,9-tetramethyl-10h-acridine Chemical compound C1=C(C)C=C2C(C)(C)C3=CC(C)=CC=C3NC2=C1 IIPRZFWOSCKSIM-UHFFFAOYSA-N 0.000 description 1
- ZLQLUHZPBRUNEC-UHFFFAOYSA-N 2,9,9-trimethyl-10H-acridine Chemical compound CC1(C2=CC=CC=C2NC=2C=CC(=CC1=2)C)C ZLQLUHZPBRUNEC-UHFFFAOYSA-N 0.000 description 1
- AYHGAQGOMUQMTR-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 AYHGAQGOMUQMTR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- 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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses an organic thermal activity delayed fluorescent material based on a2, 10' -biacridine derivative and application thereof. The 2,10 '-biacridine derivative is obtained by coupling acridine derivatives through self molecules, and the 2,10' -biacridine derivative is connected with different acceptor units through N atoms to construct a donor-acceptor-donor and donor-acceptor type organic thermal activity delayed fluorescent material. The material has better luminous performance and can be used for organic electroluminescent devices with better luminous performance.
Description
Technical Field
The invention relates to an organic Thermal Activity Delayed Fluorescence (TADF) material, in particular to a donor unit of a2, 10 '-biacridine derivative, and also relates to an organic thermal activity delayed fluorescence material with a donor-acceptor-donor (D-A-D)/donor-acceptor (D-A) structure, which is obtained by N coupling of the 2,10' -biacridine donor unit through an acceptor unit, and an application of the material as a light-emitting layer material of an organic electroluminescent diode, belonging to the technical field of fluorescence materials.
Technical Field
Organic electroluminescent diodes (OLEDs) are considered to be the ultimate technology for flat panel displays due to their high brightness, low power consumption, large area fabrication, and flexible display capabilities. Over thirty years of development, the development of OLEDs has been with great success. Currently, small active matrix oled (amoled) displays are widely used in smart phones. Large-sized AMOLED (55 inch) televisions have also been commercialized. Organic electroluminescent materials have been the research focus of researchers in research institutes and enterprises as the core foundation of OLEDs. Organic electroluminescent materials are mainly classified into two categories according to the difference of electron transition: fluorescent light emitting materials (singlet) and phosphorescent light emitting materials (triplet). According to the spin statistics theory, the ratio of excited singlet state to excited triplet state is 3:1, that is, in electroluminescence, the fluorescent material only utilizes singlet exciton luminescence, and the theoretical internal quantum efficiency is 25%, which is the root cause of low efficiency of OLEDs. In order to improve the efficiency of the device, singlet excitons and triplet excitons are utilized to emit light, and in recent years, phosphorescent materials containing heavy metal atoms are gaining favor from researchers. The phosphorescence material can theoretically reach 100% internal quantum efficiency due to the strong spin-orbit coupling of heavy metal atoms. However, the lifetime of the triplet excited state of phosphorescent materials is too long resulting in severe attenuation of the efficiency of OLEDs with increasing current density; the high-efficiency phosphorescent material is mainly based on a complex of metallic iridium (Ir) and metallic platinum (Pt), and the selection range is narrow; blue phosphorescent material and white phosphorescent material are absent; more importantly, these phosphorescent materials contain rare noble metals, which causes problems such as high material cost and environmental pollution. In order to solve these scientific problems of the conventional organic electroluminescent materials and to improve the efficiency of OLEDs, the development of new organic electroluminescent materials is urgent.
In 2009, Adachi et al, kyushu university, japan, demonstrated for the first time the use of Thermally Active Delayed Fluorescence (TADF) materials in OLEDs, which has brought a tremendous revolution to the research of OLEDs. Thermally activated delayed fluorescence (E-type delayed fluorescence) refers to the first excited singlet S1And first excited triplet state T1Energy difference (Delta E)ST) Smaller (less than or equal to 42kJ/mol), T1The state can obtain certain heat energy from the environment (more than or equal to 300K) and then reach S with higher energy1State. Warp beam T1Newly formed S1The state still emits fluorescence with the original fluorescence quantum efficiency. The TADF material combines the advantages of the traditional fluorescent material and the phosphorescent material, fully utilizes the singlet state and triplet state exciton luminescence, and has the theoretical internal quantum efficiency of 100 percent. The TADF material does not contain heavy metal, reduces the material cost, meets the development requirements of energy conservation and environmental protection, and is known as a third type organic electroluminescent material. More recently, TADF materials based on purely organic compounds have received considerable attention from researchers. However, the donor units constituting the organic TADF are very few in kind, and basically have single structures such as carbazole, triphenylamine, acridine, phenothiazine and the like. Therefore, efforts to develop new donor units of organic TADF are of great significance in promoting the development and commercialization of TADF.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a2, 10' -biacridine derivative obtained by coupling an acridine derivative, which has stronger electron-donating capability relative to acridine and the like, has a larger steric hindrance structure and is a donor unit with excellent performance.
The invention also aims to provide a series of donor-acceptor-type or donor-acceptor-type organic thermal activity delayed fluorescent materials (TADF materials) with better luminescence properties, which are constructed by using the 2,10' -biacridine derivative as an electron donor unit and an organic electron-withdrawing group.
The third purpose of the invention is to provide the application of the organic thermal activity delay fluorescent material as the material of the light-emitting layer of the organic electroluminescent diode, and an organic electroluminescent device with excellent light-emitting performance can be obtained.
In order to achieve the above technical objects, the present invention provides a2, 10' -biacridine derivative having the structure of formula 1:
wherein,
r is selected from hydrogen, alkyl, alkoxy or halogen substituent.
The 2,10 '-biacridine derivative is formed by coupling two molecules of acridine through self molecules, wherein the two molecules of acridine are connected with the N atom of another molecule of 9, 9-dimethylacridine derivative on the No. 2 position of the 9, 9-dimethylacridine derivative to form a2, 10' -biacridine unit, the electron-donating capability of the acridine unit is obviously improved, and the acridine unit has larger steric hindrance and is a better donor unit.
Preferably, R may be generally hydrogen or an electron donating group. The electron-donating group can be neutral electron-donating group with weak electron-donating ability, such as halogen, and the halogen is fluorine, chlorine, bromine, etc. The electron donating group may be a weak electron donating group such as alkyl, preferably C1～C8The alkyl group of (a) may be a straight-chain alkyl group or a branched-chain alkyl group. The electron donating group can be an electron donating groupAlkoxy with a high electron capacity, preferably C1～C8Alkoxy groups such as methoxy. Ethoxy and the like.
The invention also provides a donor-receptor-donor type or donor-receptor type organic thermal activity delayed fluorescent material which is formed by the 2,10' -biacridine derivative through an N-coupled organic receptor unit.
Preferred acceptor units have the following structural units:
wherein,
X1is C or N;
X2is C or S;
X3is Se or S.
The preferred acceptor unit and the donor unit of the invention have matched energy levels, and the donor-acceptor-donor type or donor-acceptor type organic thermal activity delayed fluorescent material with good performance can be obtained.
Preferred donor-acceptor-type or donor-acceptor-type organic thermal activity delayed fluorescent materials have a structure of formula 2, formula 3, or formula 4:
a is
A structural unit;
a1 is
A structural unit;
a2 is
A structural unit;
wherein,
X1is C or N;
X2is C or S;
X3is Se or S;
r is selected from hydrogen, alkyl, alkoxy or halogen substituent.
The invention also provides application of the donor-acceptor-donor type or donor-acceptor type organic thermal activity delayed fluorescent material, and the donor-acceptor type or donor-acceptor type organic thermal activity delayed fluorescent material is used as a luminescent layer material of an organic electroluminescent diode for an organic electroluminescent device.
The invention takes 2,10' -biacridine derivatives as donor units, and introduces different electron-withdrawing groups on N atoms of the 2,10' -biacridine derivatives so as to construct the organic TADF material with D-A-D or D-A structure taking the 2,10' -biacridine derivatives as donor units.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the existing 9, 9-dimethylacridine, the 2,10' -biacridine derivative has stronger electron-donating capability and larger steric hindrance structure, is beneficial to constructing a luminescent material with better performance, and expands the types of donor units of organic TADF materials.
The invention utilizes 2,10' -biacridine derivatives to construct a series of donor-acceptor-donor type or donor-acceptor type organic thermal activity delayed fluorescent material organic TADF materials with better luminous performance by introducing different electron-withdrawing groups on N atoms.
The invention uses the organic TADF material constructed by 2,10' -biacridine derivative as the luminescent layer material of the organic electroluminescent diode for the organic electroluminescent device. Compared with acridine derivatives, 2,10' biacridine has higher HOMO energy level, so that the hole transport capability is better, the hole and electron are better compounded in a light-emitting layer, the exciton generation rate is effectively improved, and the better light-emitting performance is obtained.
Drawings
FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of compound M1 in toluene, obtained in example 2 of the present invention.
FIG. 2 is a diagram showing an ultraviolet-visible absorption spectrum of compound M2 in toluene, obtained in example 2 of the present invention.
FIG. 3 is a chart of the UV/VIS absorption spectrum of compound M3 in toluene obtained in example 2 of the present invention.
FIG. 4 is a chart of the UV-VIS absorption spectrum of compound M4 in toluene obtained in example 2 of the present invention.
FIG. 5 shows the UV/VIS absorption spectrum of compound M5 in toluene prepared in example 2 of the present invention.
FIG. 6 is a photoluminescence spectrum of a compound M1 prepared in example 2 of the present invention in toluene.
FIG. 7 is a photoluminescence spectrum of a compound M2 prepared in example 2 of the present invention in toluene.
FIG. 8 is a photoluminescence spectrum of a compound M3 prepared in example 2 of the present invention in toluene.
Detailed Description
The following specific examples are intended to further illustrate the invention, but these specific embodiments do not limit the scope of the invention in any way.
Example 1
Preparation of 2,10' -biacridine:
in a 100mL two-necked flask were added 9, 9-dimethylacridine (600mg,2.97mmol), tert-butylphosphine (30mg,0.148mmol), palladium on carbon (10%) (94mg,0.89mmol), potassium hydroxide (166mg,2.97mmol) and toluene (60mL) in that order, and the mixture was refluxed under nitrogen for 24 h. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3×30mL) of the extract; the organic layer was washed with water (50mL), dried, and distilled under reduced pressure to remove the solvent; the residue was purified by petroleum ether: column chromatography with dichloromethane (V: V ═ 5:1) as eluent gave 120mg (yield: 19%) of a pale yellow solid.1H NMR(300MHz,DMSO-d6)9.17(s,1H),7.47-7.44(m,2H),7.37(d,J＝9.0Hz,1H),7.24(d,J＝3.0Hz,1H),7.13-7.04(m,2H),7.00-6.92(m,3H),6.88-6.82(m,4H),6.23-6.20(m,2H),1.61(s,6H),1.49(s,6H).
Example 2
Preparation of 2',7,7' -trimethyl-2, 10' -biacridine:
in a 100mL two-necked flask were added 2,7,9, 9-tetramethylacridine (600mg,2.53mmol), 2,9, 9-trimethylacridine (600mg,2.69mmol), tert-butylphosphine (65mg,0.323mmol), palladium on carbon (10%) (172mg,0.161mmol), potassium hydroxide (708mg,12.65mmol) and toluene (60mL) in this order, and the mixture was refluxed under nitrogen for 24 hours. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL), the organic layer was washed with water (50mL), dried, and the solvent was removed by distillation under the reduced pressure, and the residue was subjected to column chromatography using petroleum ether and dichloromethane (V: V ═ 4:1) as an eluent to give 232mg (yield: 20%) of a pale yellow solid.1H NMR(300MHz,DMSO-d6)9.17(s,1H),7.47-7.44(m,2H),7.37(d,J＝9.0Hz,1H),7.24(d,J＝3.0Hz,1H),7.13-7.04(m,2H),7.00-6.92(s,1H),6.88-6.82(m,3H),6.23-6.20(m,2H),2.38(s,6H),2.26(s,3H),1.61(s,6H),1.49(s,6H).
Example 3
Preparation of compound M1-M5, the synthetic route is shown in the following reaction scheme:
preparation of Compound M1
In a 100mL two-necked flask were added 2,10' -biacridine (161mg,0.39mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (100mg,0.2576mmol), and t-butylphosphine (4.1680mg, 0) in that order.0206mmol), sodium tert-butoxide (99mg,1.03mmol), tris (dibenzylideneacetone) dipalladium (9.4mg,0.0103mmol) and toluene (60mL), the mixture was refluxed under nitrogen for 24 h. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL), the organic layer was washed with water (50mL), dried, and the solvent was removed by distillation under reduced pressure, and the residue was subjected to column chromatography using petroleum ether and dichloromethane (V: 5:1) as an eluent to give 89mg (yield: 48%) of a pale green solid.1H NMR(400MHz,CDCl3)9.08(d,J＝8.0Hz,2H),8.84-8.82(m,4H),7.69-7.59(m,8H),7.53-7.51(m,1H),7.46-7.44(m,2H),7.40(d,J＝2.3Hz,1H),7.08-6.97(m,4H),6.93-6.89(m,3H),6.61(d,J＝8.0Hz,1H),6.47-6.45(m,1H),6.36(d,J＝8.0Hz,2H),1.72(s,12H).
Preparation of compound M2:
in a 100mL two-necked flask were added 2,10 '-biacridine (255mg,0.6116mmol), 4' -dibromodiphenylsulfone (100mg,0.2659mmol), tri-tert-butylphosphine (6.4560mg, 31.91. mu. mol), sodium tert-butoxide (102mg,1.0621mmol), tris (dibenzylideneacetone) dipalladium (14.6mg, 15.95. mu. mol), and toluene (60mL) in that order, and the mixture was refluxed under nitrogen for 24 h. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL), and the organic layer was washed with water (50mL), dried, and distilled under reduced pressure to remove the solvent, and the residue was subjected to column chromatography using petroleum ether and dichloromethane (V: V ═ 2:1) as an eluent to give 100mg (yield: 36%) of a pale green solid.1H NMR(300MHz,CDCl3)8.37-8.32(m,4H),7.72-7.68(m,4H),7.51-7.50(m,2H),7.46(d,J＝4.0Hz,2H),7.43(d,J＝1.9Hz,2H),7.39(d,J＝2.3Hz,2H),7.06–7.01(m,4H),6.98-6.87(m,10H),6.52(d,J＝9.0Hz,2H),6.36-6.33(m,2H),6.30-6.27(m,4H),1.69(s,12H),1.66(s,12H).
Preparation of compound M3:
in a 100mL two-necked flask were added 2,10 '-biacridine (282mg,0.6765mmol), 4' -dibromobenzophenone (100mg,0.2941mmol), tri-tert-butylphosphine (7.14mg, 35.29. mu. mol), sodium tert-butoxide (113mg,1.1765mmol), tris (dibenzylideneacetone) dipalladium (16mg, 17.647. mu. mol), and toluene (60mL) in this order, and the mixture was refluxed under nitrogen for 24 hours. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL) extraction(ii) a The organic layer was washed with water (50mL), dried, and distilled under reduced pressure to remove the solvent, and the residue was washed with petroleum ether: column chromatography with dichloromethane (V: V ═ 3:1) as eluent gave 200mg (yield: 67%) of a yellow solid.1H NMR(300MHz,CDCl3)8.24(d,J＝9.0Hz,4H),7.66(d,J＝9.0Hz,4H),7.53-7.50(m,2H),7.47-7.44(m,4H),7.40(d,J＝3.0Hz,2H),7.09-7.03(m,4H),7.01-6.88(m,10H),6.58(d,J＝9.0Hz,2H),6.45-6.41(m,2H),6.35-6.32(m,4H),1.70(s,24H).
Preparation of compound M4:
in a 100mL two-necked flask were added 2,10' -biacridine (189mg,0.4528mmol), 2-bromoanthraquinone (100mg,0.3483mmol), tri-tert-butylphosphine (5.64mg, 27.86. mu. mol), sodium tert-butoxide (134mg,1.393mmol), tris (dibenzylideneacetone) dipalladium (12.7mg,13.93mmol), and toluene (60mL) in that order, and the mixture was refluxed under nitrogen for 24 h. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL), and the organic layer was washed with water (50mL), dried, and distilled under reduced pressure to remove the solvent, and the residue was subjected to column chromatography using petroleum ether and dichloromethane (V: 5:1) as an eluent to obtain 80mg of a red solid (yield: 37%).1H NMR(300MHz,CDCl3)8.62(d,J＝9.0Hz,2H),8.43(d,J＝2.0Hz,2H),8.41-8.35(m,4H),7.93(d,J＝3.0Hz,1H),7.90(d,J＝3.0Hz,1H),7.88-7.85(m,4H),7.5-7.51(m,2H),7.46(d,J＝1.6Hz,2H),7.43(d,J＝3.0Hz,2H),7.41(d,J＝3.0Hz,2H),7.07-7.04(m,4H),7.01(d,J＝3.0Hz,1H),6.99(d,J＝1.6Hz,2H),6.97-6.93(m,4H),6.92-6.91(m,3H),6.89(d,J＝3.0Hz,1H),6.55(d,J＝9.0Hz,2H),6.43-6.40(m,2H),6.34-6.40(m,4H),1.70(s,24H).
Preparation of compound M5:
in a 100mL two-necked flask were added 2,10' -biacridine (262mg,0.6284mmol), 2, 6-bromoanthraquinone (100mg,0.2732mmol), tri-tert-butylphosphine (6.63mg, 32.79. mu. mol), sodium tert-butoxide (105mg,1.0929mmol), tris (dibenzylideneacetone) dipalladium (15.01mg, 16.39. mu. mol), and toluene (60mL) in this order, and the mixture was refluxed under nitrogen for 24 h. Cooling the reaction liquid to room temperature, and using CH for the mixture2Cl2(3 × 30mL), the organic layer was washed with water (50mL), dried, and the solvent was distilled off under reduced pressure, and the residue was extracted with petroleum ether and dichloromethane (V: 4):1) column chromatography was performed as an eluent to give 91mg of a dark red solid (yield: 32%).1H NMR(300MHz,CDCl3)8.65(d,J＝9.0Hz,2H),8.49(d,J＝2.1Hz,2H),7.97-7.95(m,2H),7.55-7.52(m,2H),7.47(d,J＝3Hz,2H),7.44-7.43(m,4H),7.10-7.06(m,4H),7.03-6.89(m,10H),6.60(d,J＝6.0Hz,2H),6.47-6.44(m,2H),6.35-6.32(m,4H),1.70(d,J＝3.0Hz,24H).
Example 4
UV-VIS absorption Spectroscopy testing of Compounds M1-M5 from example 2.
Dissolving compounds M1-M5 in toluene to obtain 10-5And M, testing the ultraviolet visible absorption spectrum of the solution. As can be seen, the UV-visible absorption spectrum of the compound M1-M5 in solution has approximately two absorption peaks: the absorption peak at short wavelengths (360nm) is mainly attributed to the transition absorption of pi-pi of the molecule; the absorption peak of long wavelength (> 370nm) is attributed to the charge transfer (ICT) transition absorption peak from donor unit to acceptor unit in the molecule.
Example 4
Photoluminescence spectroscopy of compound M1-M5 of example 2. Compound M1-3 was dissolved in toluene to prepare 10-5M solution, and testing the photoluminescence spectrum of the solution. FIGS. 6-8 show photoluminescence spectra of compounds M1-M5 in solution. It can be seen from fig. 6 to 8 that the emission color can be controlled by adjusting the LUMO level of the acceptor.
As can be seen, under the excitation of light, the maximum emission peak of the compound M1 in the toluene solution is 581 nm; the maximum emission peak of compound M2 in toluene solution was 535 nm; the maximum emission peaks of compound M3 in toluene solution were 593nm, respectively. The maximum emission peaks of compounds M1, M3 in the toluene solution exhibited a significant red shift compared to compound M1, probably due to the lower LUMO levels of the receptors of compounds M1 and M3 compared to the receptor of compound M2, resulting in a red shift of the photoluminescence spectrum.
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.
Claims (2)
1. A donor-acceptor-donor-or donor-acceptor-type organic thermal activity delayed fluorescent material, characterized in that:
the donor-acceptor-donor type or donor-acceptor type organic thermal activity delayed fluorescent material has a structure of a formula 3 or a formula 4:
formula 3
Formula 4
A structural unit;
wherein,
X2is C or S;
X3is Se or S;
r is selected from hydrogen, alkyl, alkoxy or halogen substituent.
2. Use of the donor-acceptor-type or donor-acceptor-type organic thermal activity delayed fluorescent material according to claim 1, characterized in that: the material is used as the material of the luminescent layer of the organic electroluminescent diode for the organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811148806.XA CN109096252B (en) | 2018-09-29 | 2018-09-29 | Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811148806.XA CN109096252B (en) | 2018-09-29 | 2018-09-29 | Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096252A CN109096252A (en) | 2018-12-28 |
| CN109096252B true CN109096252B (en) | 2020-09-22 |
Family
ID=64868017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811148806.XA Active CN109096252B (en) | 2018-09-29 | 2018-09-29 | Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096252B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172035A (en) * | 2019-05-10 | 2019-08-27 | 安徽秀朗新材料科技有限公司 | The preparation and its application of thermal activities delayed fluorescence material based on bioxindol unit |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140070450A (en) * | 2012-11-30 | 2014-06-10 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
| CN106380454A (en) * | 2016-08-16 | 2017-02-08 | 盐城工学院 | Organic electroluminescence materials, a luminescent device and a manufacturing method of the device |
| CN106661001A (en) * | 2014-05-14 | 2017-05-10 | 哈佛学院院长等 | Organic light-emitting diode materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102668690B1 (en) * | 2016-08-02 | 2024-05-28 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light-emitting device comprising the same |
-
2018
- 2018-09-29 CN CN201811148806.XA patent/CN109096252B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140070450A (en) * | 2012-11-30 | 2014-06-10 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
| CN106661001A (en) * | 2014-05-14 | 2017-05-10 | 哈佛学院院长等 | Organic light-emitting diode materials |
| CN106380454A (en) * | 2016-08-16 | 2017-02-08 | 盐城工学院 | Organic electroluminescence materials, a luminescent device and a manufacturing method of the device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096252A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8003227B2 (en) | Organic electroluminescent element | |
| EP1499624B1 (en) | Electroluminescent materials | |
| KR101802526B1 (en) | Materials for organic electroluminescence devices | |
| Wang et al. | Synthesis, photoluminescence and electroluminescence of new 1 H-pyrazolo [3, 4-b] quinoxaline derivatives | |
| KR101948334B1 (en) | Materials for electronic devices | |
| EP3006433B1 (en) | Compound, organic light emitting element comprising same, and display device comprising organic light emitting element | |
| EP2177586A1 (en) | Luminescent material and organic electroluminescent device using the same | |
| CN101508649A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20120066390A (en) | Anthracene deriva tives and organic light-emitting diode including the same | |
| CN111253332A (en) | Organic compound, preparation method thereof and application of organic compound in OLED | |
| JP4865551B2 (en) | Organic electroluminescence device | |
| CN112898323A (en) | Compound, application thereof and organic electroluminescent device comprising compound | |
| CN111320638A (en) | Star-shaped blue thermal activity delayed fluorescent material based on triazolotriazine and application thereof | |
| KR101765199B1 (en) | Iridium complex compounds and organic electroluminescent device using the same | |
| CN113004292A (en) | Main luminescent material based on triazolotriazine and application thereof | |
| CN110571338B (en) | Composition for organic electronic device and organic electronic device using the same | |
| CN113015734A (en) | Heterocyclic compound and organic light emitting device including the same | |
| CN109096252B (en) | Organic thermal activity delayed fluorescent material based on 2,10' -biacridine derivative and application thereof | |
| CN113149864B (en) | Synthesis and application of thermal activity delay fluorescent material based on indeno [2,1-a ] indene condensed ring unit | |
| CN107880031B (en) | Compound with aza-benzene as core and application thereof in organic electroluminescent device | |
| JP2007254312A (en) | Organic compound and organic electroluminescent element using the same | |
| CN110183361B (en) | Construction and application of cross-shaped thermal activity delay fluorescent material | |
| CN110759935B (en) | Blue thermal activity delayed fluorescent material based on fluorine boron complex and application thereof | |
| CN113861206B (en) | Blue electroluminescent material and synthesis method and application thereof | |
| CN110615783A (en) | Electroluminescent material with pyrazinoindenone as electron acceptor 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 |