CN106496278A - The electroluminescent device of complex of iridium and its preparation method and application complex of iridium - Google Patents
The electroluminescent device of complex of iridium and its preparation method and application complex of iridium Download PDFInfo
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- CN106496278A CN106496278A CN201610800876.3A CN201610800876A CN106496278A CN 106496278 A CN106496278 A CN 106496278A CN 201610800876 A CN201610800876 A CN 201610800876A CN 106496278 A CN106496278 A CN 106496278A
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- Prior art keywords
- bis
- iridium
- complex
- trifluoromethyl pyridine
- trifluoromethyl
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 57
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 44
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 21
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZMJRUUBDMPKHJS-UHFFFAOYSA-N 2-phenyl-1,3,4-thiadiazole Chemical class S1C=NN=C1C1=CC=CC=C1 ZMJRUUBDMPKHJS-UHFFFAOYSA-N 0.000 claims abstract description 8
- NZFDZFJVWFDFQV-UHFFFAOYSA-N 2,4-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=NC(C(F)(F)F)=C1 NZFDZFJVWFDFQV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000006471 dimerization reaction Methods 0.000 claims description 7
- 150000003222 pyridines Chemical class 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- RRNXYHYDSDAOFW-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C(F)(F)F RRNXYHYDSDAOFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 3
- -1 iridium Piperidine derivatives Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 2
- 125000006617 triphenylamine group Chemical class 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 241001597008 Nomeidae Species 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- YJLPIKFDEXHCNQ-UHFFFAOYSA-N iridium;quinoline Chemical compound [Ir].N1=CC=CC2=CC=CC=C21 YJLPIKFDEXHCNQ-UHFFFAOYSA-N 0.000 claims 1
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical class FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 abstract description 10
- XRFFUVUJIBWJII-UHFFFAOYSA-N 5-[(6,7-dimethoxyquinazolin-4-yl)amino]-2-methylphenol Chemical compound C=12C=C(OC)C(OC)=CC2=NC=NC=1NC1=CC=C(C)C(O)=C1 XRFFUVUJIBWJII-UHFFFAOYSA-N 0.000 abstract 1
- 150000004867 thiadiazoles Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 18
- 238000005401 electroluminescence Methods 0.000 description 13
- 150000003246 quinazolines Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound 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 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005762 2-bromopyridine Chemical class 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RQQDJYROSYLPPK-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C21.N1=CC=CC2=CC=CC=C21 Chemical compound N1=CC=CC2=CC=CC=C21.N1=CC=CC2=CC=CC=C21 RQQDJYROSYLPPK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 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
- 230000006837 decompression Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to 2 (5 phenyl 1, 3, 4 thiadiazoles 2) phenol or 2 (5 (3 pyridine) bases 1, 3, 2) phenol is assistant ligand to 4 thiadiazoles, with 2 (4, 6 two trifluoromethyl pyridines, 3) quinoline, 2 (4, 6 two trifluoromethyl pyridines, 4) quinoline, 2 (4, 6 two trifluoromethyl pyridines, 3) isoquinolin, 2 (4, 6 two trifluoromethyl pyridines, 4) isoquinolin, 2 (4, 6 two trifluoromethyl pyridines, 3) quinazoline, 2 (4, 6 two trifluoromethyl pyridines, 4) quinazoline and 2 (4, 6 two trifluoromethyl pyridines, 3) phthalazines, 2 (4, the complex of iridium of part based on 6 two trifluoromethyl pyridines, 4) in phthalazine derivatives any one.This kind of complex of iridium can adjust the luminous intensity and efficiency of coordination compound in red wavelength range.
Description
【Technical field】
The present invention relates to organic electroluminescence device technical field, more particularly to a class complex of iridium and preparation method thereof and
Apply the electroluminescent device of the complex of iridium.
【Background technology】
Under the overall background that global energy requirements are growing and ecological environment causes anxiety, national governments greatly develop base in succession
In high-tech energy sustainability technology and industry.Organic electroluminescence device (OLEDs) is because its visual angle is wide, brightness is high, energy consumption
Low and many advantages, such as flexible device can be prepared, and receive much attention, it is referred to as dominating the following key technology for showing the world.Closely
Nian Lai, numerous studies show, in numerous heavy metal element coordination compounds, complex of iridium be considered as OLEDs phosphor materials most
Ideal chose.There is 5d76s2The iridium atom of outer electronic structure after formation+trivalent cation, with 5d6Electron configuration, has
Stable hexa-coordinate octahedral structure, makes material that there is higher chemical stability and heat stability.Meanwhile, Ir (III) has
Larger spin orbit coupling constant (ξ=3909cm-1), be conducive to improving the interior quantum yield of coordination compound and reducing the luminous longevity
Life, so that improve the overall performance of luminescent device.
Used as phosphor material, complex of iridium typically has Microsecond grade, easily causes the triplet-triplet of complex of iridium
And the phosphorescence of triplet-intensify between son is quenched.In addition, in current conventional material, the hole of hole mobile material
Electron mobility of the mobility far above electron transport material, and conventional material of main part is also based on hole transport, this can lead
The hole of great quantities of spare is caused in the aggregation of luminescent layer and electric transmission bed boundary.These factors can all cause the reduction of efficiency and tight
The efficiency roll-off of weight.Research shows, if complex of iridium has higher electron transport ability, can effectively increase electronics and exist
The transmission and distribution of luminescent layer, the region for widening electron-hole, the quantity in balance electronic-hole pair, greatly improve device
Efficiency, reduces roll-offing for efficiency.
Therefore, it is necessary to provide a kind of while complex of iridium with high-luminous-efficiency and electron mobility.
【Content of the invention】
It is an object of the invention to provide a class contain new main part, with 2- (5- phenyl -1,3,4- thiadiazoles -2-)
Phenol or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -2-) phenol complexes of red light iridium and its preparation side for assistant ligand
Method, such coordination compound can be applied in organic electroluminescence device as the centre of luminescence.
The present invention provides a kind of complex of iridium, and which includes four main parts and an assistant ligand；The main part is 2-
(4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline, 2- (4,6- bis- trifluoromethyl pyrroles
Pyridine -3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline,
2- (4,6- bis- trifluoromethyl pyridine -4-) quinazolines and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- trifluoros
Picoline -4-) any one in phthalazine derivatives, the assistant ligand is 2- (5- phenyl -1,3,4- thiadiazoles -2-) benzene
Phenol or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -2-) phenol.
Preferably, in the main part with iridium with the pyridine derivate that carbon atom is coordinated it is：
Preferably, quinoline, isoquinolin, quinazoline and the phthalazine derivatives choosing being coordinated with nitrogen-atoms with iridium in the main part
From：In any one.
Preferably, the complex of iridium has one of following structure：
A kind of preparation method of complex of iridium is provided in the present invention：By the iridium dimerization bridging coordination compound containing four main parts
Mix with assistant ligand and sodium carbonate；Wherein, the main part is 2- (4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6-
Two trifluoromethyl pyridine -4-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridines -
4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinazolines and 2-
Any one in (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives；
Cellosolvo solution being added, reacting by heating being carried out at 120-140 DEG C, response time 12-48h is cooled to room temperature, decompression
Solvent is distilled off, then is extracted with dichloromethane, concentration, through column chromatography for separation, obtains the crude product of coordination compound, obtained through distillation pure
Complex of iridium.
Preferably, the mol ratio of the iridium dimerization bridging coordination compound, assistant ligand and sodium carbonate is 1: 2: 5.
The present invention also provides a kind of electroluminescent device of the application complex of iridium, and which includes substrate, anode, hole transport
Layer, organic luminous layer, electron transfer layer and negative electrode, the substrate are glass, and anode material is tin indium oxide (ITO)；Hole passes
Defeated layer uses 4,4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyls) aniline (TAPC), electron transport layer materials use 3,3 '-
(5 '-(3- (pyridin-3-yl) phenyl)-[1,1 '：3 ', 1 "-triphenyl] -3,3 "-diyl) two pyridines (TmPyPB), negative electrode employing
LiF/Al.Double emitting layers of the organic luminous layer using doped structure, material of main part is to use 4,4 ', 4 respectively "-three (carbazole -9- bases)
Triphenylamine (TcTa) and double (3- (9- carbazyls) phenyl) pyridines (26DCzPPy) of 2,6-, selected luminescent material is above-mentioned
Complex of iridium, mass fraction 5wt%.
Beneficial effects of the present invention：The complex of iridium that the present invention is provided has high luminous efficiency, electron mobility height and changes
The characteristics of learning stable in properties, easy sublimation purification.The preparation method of the complex of iridium is simple, and yield is higher.Due to azacyclo-
Introduce, the electronic transmission performance of coordination compound can Effective Regulation, be the design of display of organic electroluminescence and lighting source
Production is provided convenience.
【Description of the drawings】
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium RIr6-01 that the present invention is provided；
Fig. 2 is used for the brightness-voltage curve of organic electroluminescence device for the complex of iridium RIr6-01 that the present invention is provided；
Fig. 3 is bent for current efficiency-brightness that the complex of iridium RIr6-01 that the present invention is provided is used for organic electroluminescence device
Line.
【Specific embodiment】
The present invention is described in further detail with reference to the accompanying drawings and examples.The term for being used in the present invention, unless
It is otherwise noted, the general implication with those of ordinary skill in the art's generally reason.
The invention discloses a kind of complexes of red light iridium, which includes four new main parts and an assistant ligand.Its
In, the assistant ligand be 2- (5- phenyl -1,3,4- thiadiazoles -2-) phenol or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -
2-) phenol.The main part is 2- (4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline
Quinoline, 2- (4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis-
Trifluoromethyl pyridine -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinazolines and 2- (4,6- bis- trifluoromethyl pyrroles
Pyridine -3-) phthalazines, any one in 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives.In the main part, and iridium
With the pyridine derivate that carbon atom is coordinated it is：Quinoline in the pyridine derivate and main part, different
Quinoline, quinazoline are different with the link position of phthalazine derivatives.The quinoline, isoquinolin, quinazoline and phthalazine derivatives are selected from： In any one.The assistant ligand be 2- (5- phenyl -1,
3,4- thiadiazoles -2-) phenol or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -2-) phenol.
The complex of iridium of the present invention has all used iridous chloride, 4,6-, bis- trifluoromethyl pyridine -3- boron in building-up process
Acid, 4,6-, bis- trifluoromethyl pyridine -4- boric acid, 2- (5- phenyl -1,3,4- thiadiazoles -2-) phenol or 2- (5- (3- pyridines) base -
1,3,4- thiadiazoles -2-) phenol etc., synthetic method is similar to.
Will be containing 2- (4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline, 2-
(4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- fluoroforms
Yl pyridines -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinazolines and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalein
Piperazine or 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives iridium dimerization bridging coordination compound and assistant ligand as main part
And sodium carbonate mixing；Cellosolvo solution being added, reacting by heating being carried out at 120-140 DEG C, response time 12-48h is cold
But to room temperature, vacuum distillation removes solvent, then is extracted with dichloromethane, and concentration, through column chromatography for separation, obtains the thick of coordination compound
Product, obtain complex of iridium through sublimation purification.Wherein, the iridium dimerization bridging coordination compound contain 2- (4,6- bis- trifluoromethyl pyridines-
3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2- (4,6-
Two trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyrroles
Pyridine -4-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines or 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazines spread out
Biological；The mol ratio of the iridium dimerization bridging coordination compound, assistant ligand and sodium carbonate is 1: 2: 5.
The complex of iridium has one of structure of numbering RIr6-01～24 as follows：
Present invention is illustrated below as a example by complex of iridium with the numbering in a wherein embodiment as RIr6-01,
Will be helpful to further understand the present invention by following embodiments, but do not limit present disclosure.
The synthetic method of coordination compound RIr6-01
2- bromopyridines (26.39mmol), 4,6-, bis- trifluoromethyl pyridines -3- boric acid (31.66mmol), four triphenyl phosphorus palladiums
(0.79mmol) it is dissolved in 100mL tetrahydrofurans with sodium carbonate (60.00mmol), 65 DEG C are reacted 24 hours, cooling adds water
And dichloromethane, organic layer concentration column chromatography obtain main part (yield is 52.24%).By main part (13.08mmol) and three
Iridium chloride (6.23mmol) is dissolved in 15mL cellosolvos, 130 DEG C of reaction 12h of mixture, is subsequently adding assistant ligand
(12.46mmol) with sodium carbonate (31.15mmol), 130 DEG C of reaction 24h are continued.System is cooled down, and is added water and dichloromethane, is had
Machine layer concentration column chromatography obtains yellow solid RIr6-01, and its yield is 40%.
The present invention with 2- (4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline,
2- (4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- trifluoros
Picoline -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -3-)
Any one in phthalazines and 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives as main part, with 2- (5- phenyl -
1,3,4- thiadiazoles -2-) phenol or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -2-) phenol is auxiliary ligand design synthesis
A series of complexes of red light iridium.By designing part or complex structure, and pass through simple chemical substituents on part
Modification, reach that regulation and control coordination compound is luminous and the purpose of electron mobility.
The azacyclo- is the group for having stronger electron-transporting, is conducive to the injection and transmission of equilbrium carrier.
The complex of iridium has higher luminous efficiency and electron mobility, after optimized checking, its preparation method letter
Single, and yield is higher.
The preparation of organic electroluminescence device
As a example by organic electroluminescence device being prepared using RIr6-01 as luminescent material below, organic electroluminescence of the present invention is described
The preparation of luminescent device.The structure of OLEDs devices includes：Substrate, anode, hole transmission layer, organic luminous layer and electric transmission
Layer/negative electrode.
In the element manufacturing of the present invention, substrate is glass, and anode material is tin indium oxide (ITO)；Hole transmission layer is used
4, [N, N- bis- (4- aminomethyl phenyls) aniline (TAPC), electron transport layer materials use 3,3 '-(5 '-(3- (pyrroles to 4 '-cyclohexyl two
Pyridine -3- bases) phenyl)-[1,1 '：3 ', 1 "-triphenyl] -3,3 "-diyl) two pyridines (TmPyPB), thickness is 60nm, evaporation speed
Rate is 0.05nm/s；Negative electrode adopts LiF/Al.Organic luminous layer using doped structure double emitting layers, it include material of main part and
Luminescent material, material of main part are to use 4,4 ', 4 respectively " double (3- (9- carbazoles of-three (carbazole -9- bases) triphenylamines (TcTa) and 2,6-
Base) phenyl) pyridine (26DCzPPy), selected luminescent material is described complex of iridium RIr6-01, and mass fraction is preferably
5wt%.
Different materials structure in the present invention is as follows：
The present invention selects a kind of HONGGUANG coordination compound to prepare organic electroluminescence device.Fig. 1, Fig. 2 and Fig. 3 is seen also,
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium that the present invention is provided, and Fig. 2 and Fig. 3 is the present invention
The complex of iridium of offer is used for the photoelectric properties of organic electroluminescence device.As shown in Figures 2 and 3, the organic electroluminescent
The startup voltage of device is 3.8V, and its maximum power efficiency and current efficiency are respectively 57.15cd/A, high-high brightness 91453cd/
m2.By studying photophysical property, show that this kind of phosphorescent iridium complex containing azacyclo- has higher device efficiency, aobvious
The field such as show and illuminate and there is actual application value.
Such phosphor material that the present invention is provided can be applied to the emission layer of phosphorescent OLED s as the centre of luminescence, by setting
Meter part or complex structure, and by modifying to the chemical substituents of the part, invention achieves regulation and control and coordinate
Thing glow color and the purpose of efficiency.
Above-described is only embodiments of the present invention, it should be noted here that for one of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to the protection model of the present invention
Enclose.
Claims (7)
1. a kind of complex of iridium, it is characterised in that including four main parts and an assistant ligand；The main part be 2- (4,
Bis- trifluoromethyl pyridine -3- of 6-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline, 2- (4,6- bis- trifluoromethyl pyridines -
3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline, 2-
(4,6- bis- trifluoromethyl pyridine -4-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- fluoroforms
Yl pyridines -4-) any one in phthalazine derivatives；The assistant ligand is 2- (5- phenyl -1,3,4- thiadiazoles -2-) phenol
Or 2- (5- (3- pyridines) base -1,3,4- thiadiazoles -2-) phenol.
2. complex of iridium according to claim 1, it is characterised in that in the main part and the pyrrole that is coordinated with carbon atom of iridium
Piperidine derivatives are：
3. complex of iridium according to claim 1, it is characterised in that in the main part and the quinoline that is coordinated with nitrogen-atoms of iridium
Quinoline, isoquinolin, quinazoline and phthalazine derivatives are selected from： In appoint
Meaning is a kind of.
4. complex of iridium according to claim 1, it is characterised in that the complex of iridium has one of following structure：
5. a kind of preparation method of the complex of iridium as described in any one of claim 1-4, it is characterised in that will be containing four masters
The iridium dimerization bridging coordination compound of part and assistant ligand and sodium carbonate mixing, the main part is 2- (4,6- bis- trifluoromethyl pyrroles
Pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinoline, 2- (4,6- bis- trifluoromethyl pyridine -3-) isoquinolin, 2-
(4,6- bis- trifluoromethyl pyridine -4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline, 2- (4,6- bis- fluoroforms
Yl pyridines -4-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazines
Any one in derivant；Cellosolvo solution is added, and reacting by heating, response time 12- is carried out at 120-140 DEG C
48h, is cooled to room temperature, and vacuum distillation removes solvent, then is extracted with dichloromethane, and concentration, through column chromatography for separation, obtains coordination compound
Crude product, through distillation obtain pure complex of iridium.
6. the preparation method of complex of iridium according to claim 5, it is characterised in that the iridium dimerization bridging coordination compound and
The mol ratio of sodium carbonate is 1: 5.
7. a kind of electroluminescent device of complex of iridium of the application as described in claim 1-4 any one, it is characterised in that bag
Substrate, anode, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode is included, the substrate is glass, the anode
Material is tin indium oxide；The hole transmission layer uses 4,4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyls) aniline, the electricity
3,3 '-(5 '-(3- (pyridin-3-yl) phenyl)-[1,1 ' of sub- transport layer materials'use：3 ', 1 "-triphenyl] -3,3 "-diyl) two
Pyridine, negative electrode adopt LiF/Al.Double emitting layers of the organic luminous layer using doped structure, material of main part is to use 4,4 ', 4 respectively "-
Three (carbazole -9- bases) triphenylamines and double (3- (9- carbazyls) phenyl) pyridines of 2,6-, selected luminescent material is that the iridium is matched somebody with somebody
Compound, mass fraction 5wt%.
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| CN108484677A (en) * | 2018-01-30 | 2018-09-04 | 瑞声光电科技(常州)有限公司 | A kind of pyridine structure contained feux rouges metal complex |
| CN110475772A (en) * | 2017-04-06 | 2019-11-19 | 巴斯夫欧洲公司 | Pyridine compounds |
| EP4112701A3 (en) * | 2021-06-08 | 2023-04-26 | University of Southern California | Molecular alignment of homoleptic iridium phosphors |
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| CN102265424A (en) * | 2008-12-26 | 2011-11-30 | 出光兴产株式会社 | Material for organic electroluminescent element and organic electroluminescent element |
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| CN102265424A (en) * | 2008-12-26 | 2011-11-30 | 出光兴产株式会社 | Material for organic electroluminescent element and organic electroluminescent element |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110475772A (en) * | 2017-04-06 | 2019-11-19 | 巴斯夫欧洲公司 | Pyridine compounds |
| CN108484677A (en) * | 2018-01-30 | 2018-09-04 | 瑞声光电科技(常州)有限公司 | A kind of pyridine structure contained feux rouges metal complex |
| EP4112701A3 (en) * | 2021-06-08 | 2023-04-26 | University of Southern California | Molecular alignment of homoleptic iridium phosphors |
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