CN106432347A - Iridium complexes, preparation method thereof and electroluminescent device using iridium complexes - Google Patents
Iridium complexes, preparation method thereof and electroluminescent device using iridium complexes Download PDFInfo
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- CN106432347A CN106432347A CN201610801221.8A CN201610801221A CN106432347A CN 106432347 A CN106432347 A CN 106432347A CN 201610801221 A CN201610801221 A CN 201610801221A CN 106432347 A CN106432347 A CN 106432347A
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 150000002503 iridium Chemical class 0.000 title abstract 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 42
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 23
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052741 iridium Inorganic materials 0.000 claims description 54
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 19
- 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 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000006471 dimerization reaction Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- -1 sun Pole Substances 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
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000006837 decompression Effects 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
- 125000004433 nitrogen atom Chemical group N* 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
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000859 sublimation Methods 0.000 abstract description 3
- 230000008022 sublimation Effects 0.000 abstract description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 abstract 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 18
- 238000005401 electroluminescence Methods 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 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
- 239000004327 boric acid Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- WVDARQFRSJYGOH-UHFFFAOYSA-N 2-bromo-1h-isoquinoline Chemical class C1=CC=C2C=CN(Br)CC2=C1 WVDARQFRSJYGOH-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- 150000005645 2-bromoquinolines 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
- 241001597008 Nomeidae Species 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction 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
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000005286 illumination Methods 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
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 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
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- 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
- 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
- H10K85/30—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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to three-element co-ligand iridium complexes with novel ligands. The ligands in molecules of the iridium complexes in the series are 2-(4,6-bis(trifluoromethyl)pyridine-3-)quinoline, 2-(4,6-bis(trifluoromethyl)pyridine-4-)quinoline, 2-(4,6-bis(trifluoromethyl)pyridine-3-)isoquinoline, 2-(4,6-bis(trifluoromethyl)pyridine-4-)isoquinoline, 2-(4,6-bis(trifluoromethyl)pyridine-3-)quinazoline, 2-(4,6-bis(trifluoromethyl)pyridine-4-)quinazoline, 2-(4,6-bis(trifluoromethyl)pyridine-3-)phthalazine and 2-(4,6-bis(trifluoromethyl)pyridine-4-)phthalazine derivatives. The novel iridium complexes have the advantages that the luminous efficiency is high, the chemical property is stable, sublimation purification is easy and the like, and besides, the performance of a device is good. The luminous intensity and efficiency of the ligands can be adjusted in the wavelength coverage of red light through a molecular structure modifying the ligands, which brings convenience to design and production of organic electroluminescent displays and lighting sources.
Description
【Technical field】
The present invention relates to organic electroluminescence device technical field, particularly relate to class complex of iridium and preparation method thereof and
Apply the luminescent device of described complex of iridium.
【Background technology】
Under the overall background that and ecological environment growing at global energy requirements 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 the plurality of advantages such as flexible device can be prepared, and receive much attention, it is referred to as to dominate the key technology in display in the future world.Closely
Nian Lai, numerous studies show, in numerous heavy metal element complexs, complex of iridium be considered as OLEDs phosphor material
Ideal chose.There is 5d76s2The iridium atom of outer electronic structure, after formation+trivalent cation, has 5d6Electron configuration, has
Stable hexa-coordinate octahedral structure, makes material have higher chemical stability and heat endurance.Meanwhile, Ir (III) has
Bigger spin orbit coupling constant (ξ=3909cm-1), be conducive to improving the interior quantum yield of complex and reduce the luminous longevity
Life, thus improve the overall performance of luminescent device.
As phosphor material, complex of iridium typically has Microsecond grade, easily causes the triplet-triplet of complex of iridium
And triplet-intensify the phosphorescence cancellation between son.In addition, in current conventional material, the hole of hole mobile material
Mobility is far above the electron mobility of electron transport material, and based on conventional material of main part is also with hole transport, this can lead
Cause the gathering at luminescent layer and electric transmission bed boundary for the hole of great quantities of spare.These factors all can 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 of luminescent layer and distribution, the region widening electron-hole, the quantity in balance electronic-hole pair, improve device greatly
Efficiency, reduces roll-offing of efficiency.
Therefore, it is necessary to provide a kind of complex of iridium with high-luminous-efficiency and electron mobility.
【Content of the invention】
It is an object of the invention to provide complexes of red light iridium and the preparation thereof that the ternary that a class contains Novel Ligands is joined altogether
Method, such complex can be applied in organic electroluminescence device as the centre of luminescence.
The present invention provides a kind of complex of iridium, and it contains three parts, described part be 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-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, in 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives
Any one, in described part and the pyridine derivate that is coordinated with carbon atom of iridium is：With iridium with
The quinoline of nitrogen-atoms coordination, isoquinolin, quinazoline and phthalazine derivatives are selected from： In any one.
Preferably, described complex of iridium has one of following structure：
The complex of iridium preparation method providing in the present invention is as follows：Will containing four 2-(4,6-bis-trifluoromethyl pyridine-
3-) base 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-trifluoromethyl
Pyridine-4-) quinazoline and 2-(4,6-bis-trifluoromethyl pyridine-3-) phthalazines, 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazines spread out
The biological iridium dimerization bridging complex as part and same part and sodium carbonate mix；Add cellosolvo solution,
Carrying out heating reaction, reaction time 12-48h at 120 140 DEG C, being cooled to room temperature, decompression is distilled off solvent, then uses dichloromethane
Alkane extracts, and concentrates, through column chromatography for separation, obtains the crude product of complex, obtains pure complex of iridium through distillation.
Preferably, the mol ratio of described iridium dimerization bridging complex, part and sodium carbonate is 1:2:5.
The present invention also provides the luminescent device of a kind of this complex of iridium of application, it include substrate, anode, hole transmission layer,
Organic luminous layer, electron transfer layer and negative electrode, described substrate is glass, and anode material is tin indium oxide (ITO)；Hole transmission layer
Using 4, [N, N-bis-(4-aminomethyl phenyl) aniline (TAPC), electron transport layer materials uses 3 to 4'-cyclohexyl two, 3'-(5'-(3-
(pyridin-3-yl) phenyl)-[1,1':3', 1 "-triphenyl]-3,3 "-diyl) two pyridines (TmPyPB), negative electrode uses LiF/Al.
Organic luminous layer uses the double emitting layers of doped structure, and material of main part is with 4,4' respectively, and 4 "-three (carbazole-9-base) triphenylamine
(TcTa) double (3-(9-carbazyl) phenyl) pyridine (26DCzPPy) of and 2,6-, selected luminescent material is that described iridium coordinates
Thing, mass fraction 5wt%.
Beneficial effects of the present invention：The complex of iridium that the present invention provides has luminous efficiency height, electron mobility is high and changes
Learn stable in properties, the feature of easy sublimation purification.The preparation method of described complex of iridium is simple, and productivity is higher.Due to azacyclo-
Introduce, the electronic transmission performance of complex can Effective Regulation, be the design of display of organic electroluminescence and lighting source
Production is provided convenience.
【Brief description】
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium RIr1-01 that the present invention provides；
Fig. 2 is used for the brightness-voltage curve of organic electroluminescence device for the complex of iridium RIr1-01 that the present invention provides；
The complex of iridium RIr1-01 that Fig. 3 provides for the present invention is bent for the current efficiency-brightness of organic electroluminescence device
Line；
【Detailed description of the invention】
With embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.The term being used in the present invention, unless
It is otherwise noted, typically there is the implication that those of ordinary skill in the art generally manage.
A kind of complex of iridium, it contains three parts, and described part is 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 pyrrole
Pyridine-4-) isoquinolin, 2-(4,6-bis-trifluoromethyl pyridine-3-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-4-) quinazoline and
Any one in 2-(4,6-bis-trifluoromethyl pyridine-3-) phthalazines, 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives
Kind, the pyridine derivate being coordinated with carbon atom with iridium in described part is：Described part neutralizes
Quinoline, isoquinolin, quinazoline and phthalazine derivatives that iridium is coordinated with nitrogen-atoms are selected from： In any one.
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-bromoquinoline derivative, 2-bromo-isoquinoline derivative, 2-bromine quinazoline derivant
With 2-bromine phthalazine derivatives 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-fluoroform
Yl pyridines-3-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-4-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-3-) phthalein
Piperazine and 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives as the iridium dimerization bridging complex of part and same part and
Sodium carbonate mixes；Add cellosolvo solution, at 120-140 DEG C, carry out heating reaction, reaction time 12-48h, cooling
To room temperature, decompression is distilled off solvent, then with dichloromethane extraction, concentrates, through column chromatography for separation, obtain the crude product of complex,
Obtain complex of iridium through sublimation purification.Wherein, described iridium dimerization bridging complex contains 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-trifluoromethyl pyridine-3-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-
4-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-3-) phthalazines and 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives,
The mol ratio of described iridium dimerization bridging complex, part and sodium carbonate is 1:2:5.
Described complex of iridium has one of following structure：
Below with a wherein embodiment, as a example by complex RIr1-01, illustrate present invention, by following embodiment
Will assist in and be further appreciated by the present invention, but do not limit present disclosure.
The synthetic method of complex RIr1-01
2-bromopyridine (26.39mmol), 4,6-bis-trifluoromethyl pyridine-3-boric acid (31.66mmol), four triphenyl phosphorus palladiums
(0.79mmol) being dissolved in 100mL oxolane with sodium carbonate (60.00mmol), 65 DEG C are reacted 24 hours, and cooling adds water
And dichloromethane, organic layer evaporating column chromatography obtains part (productivity is 56.33%).By part (13.08mmol) and tri-chlorination
Iridium (6.23mmol) is dissolved in 15mL cellosolvo, and 130 DEG C of mixture reacts 12h, is subsequently adding part
(12.46mmol) with sodium carbonate (31.15mmol), 130 DEG C of reaction 24h are continued.System cools down, and adds water and dichloromethane, has
Machine layer evaporating column chromatographs to obtain yellow solid RIr1-01, and its productivity is 51%.
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-trifluoro
Picoline-3-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-4-) quinazoline, 2-(4,6-bis-trifluoromethyl pyridine-3-)
Phthalazines and 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives have synthesized a series of ruddiness iridium coordinated as part, designs
Thing.By design part or complex structure, and by the modification of simple chemical substituents on part, reach regulation and control and coordinate
The luminous purpose with electron mobility of thing.
Described azacyclo-is all the group having stronger electron-transporting, beneficially the injection of equilbrium carrier and transmission.
Described complex of iridium has higher luminous efficiency and electron mobility, after optimized checking, and its preparation method letter
Single, and productivity is higher.
The preparation of organic electroluminescence device
As a example by preparing organic electroluminescence device using RIr1-01 as luminescent material below, organic electroluminescence of the present invention is described
The preparation of luminescent device.The structure of OLEDs device 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 uses
[N, N-bis-(4-aminomethyl phenyl) aniline (TAPC), electron transport layer materials uses 3 to 4,4'-cyclohexyl two, 3'-(5'-(3-(pyrrole
Pyridine-3-base) phenyl)-[1,1':3', 1 "-triphenyl]-3,3 "-diyl) two pyridines (TmPyPB), thickness is 60nm, evaporation speed
Rate is 0.05nm/s；Negative electrode uses LiF/Al.Organic luminous layer uses the double emitting layers of doped structure, and material of main part is to use respectively
4,4', 4 "-three (carbazole-9-base) triphenylamine (TcTa) and 2, double (3-(9-carbazyl) phenyl) pyridine (26DCzPPy) of 6-, institute
The luminescent material selected is described complex of iridium RIr1-01, mass fraction 5wt%.
Different materials structure in the present invention is as follows：
The present invention selects a kind of ruddiness complex to prepare organic electroluminescence device.See also Fig. 1, Fig. 2 and Fig. 3,
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium that the present invention provides, Fig. 2 and Fig. 3 is the present invention
The complex of iridium providing is for the photoelectric properties of organic electroluminescence device.As shown in Figures 2 and 3, described organic electroluminescent
The startup voltage of device is 3.6V, and its maximum power efficiency and current efficiency are respectively 60.07cd/A, high-high brightness 97589cd/
m2.By research photophysical property, show that this kind of phosphorescent iridium complex containing azacyclo-has higher device efficiency, showing
Show and the field such as illumination has actual application value.
Such phosphor material that the present invention provides 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 the chemical substituents of described part is modified, 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 those 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 (5)
1. a complex of iridium, it is characterised in that it contains three parts, described part be 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-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, in 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives
Any one, in described part and the pyridine derivate that is coordinated with carbon atom of iridium is：With iridium with
The quinoline of nitrogen-atoms coordination, isoquinolin, quinazoline and phthalazine derivatives are selected from： In any one.
2. complex of iridium according to claim 1, it is characterised in that described complex of iridium has one of following structure：
3. the preparation method of a complex of iridium, it is characterised in that by the iridium dimerization bridging complex containing four parts and joining
Body and sodium carbonate mixing, described part be 2-(4,6-bis-trifluoromethyl pyridine-3-) quinoline, 2-(4,6-bis-trifluoromethyl pyridines-
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-trifluoromethyl pyridine-4-) quinazoline and 2-(4,6-bis-trifluoromethyl
Pyridine-3-) phthalazines, any one in 2-(4,6-bis-trifluoromethyl pyridine-4-) phthalazine derivatives；Add cellosolvo
Solution, carries out heating reaction, reaction time 12-48h at 120 140 DEG C, is cooled to room temperature, and decompression is distilled off solvent, then
With dichloromethane extraction, concentrate, through column chromatography for separation, obtain the crude product of complex, obtain pure complex of iridium through distillation.
4. the preparation method of complex of iridium according to claim 3, it is characterised in that described iridium dimerization bridging complex and
The mol ratio of sodium carbonate is 1:5.
5. an electroluminescent device for application complex of iridium as described in claim 1-2 any one, it includes substrate, sun
Pole, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode, described substrate is glass, and anode material is tin indium oxide；
Hole transmission layer uses 4, and [N, N-bis-(4-aminomethyl phenyl) aniline, electron transport layer materials uses 3,3'-to 4'-cyclohexyl two
(5'-(3-(pyridin-3-yl) phenyl)-[1,1':3', 1 "-triphenyl]-3,3 "-diyl) two pyridines, negative electrode uses LiF/Al.
Organic luminous layer uses the double emitting layers of doped structure, and material of main part is with 4,4' respectively, and 4 "-three (carbazole-9-base) triphenylamine
With 2, double (3-(9-carbazyl) phenyl) pyridine of 6-, selected luminescent material is complex of iridium, 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 |
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