CN106432351A - Iridium complexes and preparation method thereof and electroluminescent devices using iridium complexes - Google Patents
Iridium complexes and preparation method thereof and electroluminescent devices using iridium complexes Download PDFInfo
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- CN106432351A CN106432351A CN201610804580.9A CN201610804580A CN106432351A CN 106432351 A CN106432351 A CN 106432351A CN 201610804580 A CN201610804580 A CN 201610804580A CN 106432351 A CN106432351 A CN 106432351A
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- iridium
- trifluoromethyl
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 150000002503 iridium Chemical class 0.000 title abstract 6
- 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 21
- 239000003446 ligand Substances 0.000 claims abstract description 18
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 55
- 229910052741 iridium Inorganic materials 0.000 claims description 53
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 150000002466 imines Chemical class 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000006471 dimerization reaction Methods 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
- 150000003222 pyridines Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- -1 iridium Piperidine derivatives Chemical class 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
- 238000000605 extraction Methods 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
- 238000002156 mixing Methods 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
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 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
- 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
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 abstract 2
- 238000005286 illumination Methods 0.000 abstract 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 17
- 238000005401 electroluminescence Methods 0.000 description 13
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012044 organic layer 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
- UJJMLGJZQGGQAZ-UHFFFAOYSA-N 2-(fluoromethyl)pyridine Chemical compound FCC1=CC=CC=N1 UJJMLGJZQGGQAZ-UHFFFAOYSA-N 0.000 description 1
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 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
- 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
- 238000005034 decoration Methods 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
- 150000003949 imides Chemical class 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
- 239000000203 mixture Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 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
- 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
- H10K50/00—Organic light-emitting devices
-
- 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
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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)
- Pyridine Compounds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a class of iridium complexes which have novel main ligands and uses tetrakis(4-trifluoromethyl-3-pyridyl)phosphonimides or tetrakis(4-trifluoromethyl-3,5-pyrimidinyl)phosphonimides as auxiliary ligands. The main ligands in the molecule of this class of iridium complexes is any one selected from 2-(4,6-bis-trifluoromethylpyridine-3-)quinoline, 2-(4,6- bis-tribenzymethylpyridine-4-)quinoline, 2-(4,6-bis-trifluoromethylpyridine-3-)isoquinoline, 2-(4,6-bis-tribenzymethylpyridine-4-)isoquinoline, 2-(4,6-(bis-trifluoromethylpyridine-3-)quinazoline, 2-(4,6-bis-tribenzymethylpyridine-4-)quinazoline, 2-(4,6-bis-tribenzymethylpyridine-3-)phthalazie and 2-(4,6-bis-tribenzymethylpyridine-4-)phthalazine derivatives. Not only the novel iridium complexes have the advantages of being high in luminous efficiency, stable in chemical properties, easy to sublimate and purify and the like, but also the electroluminescent devices using the iridium complexes are excellent in the performance. By modifying the molecular structure of the ligands, it is possible to adjust the luminous intensity and efficiency of the complexes in the red wavelength range, and the design and production of both organic electroluminescent displays and illumination light sources are facilitated.
Description
【Technical field】
The present invention relates to organic electroluminescence device technical field, more particularly, to one class complex of iridium and preparation method thereof and
Apply the electroluminescent device of this 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 to dominate the key technology in the following display world.Closely
Nian Lai, numerous studies show, in numerous heavy metal element coordination compounds, 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, its tool
There is stable hexa-coordinate octahedral structure, make material have higher chemical stability and heat stability.Meanwhile, Ir (III) tool
There is 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, 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 the phosphorescence of triplet-intensify between son is quenched.In addition, in current conventional material, the hole of hole mobile material
Mobility is far above the electron mobility of electron transport material, and conventional material of main part is also based on hole transport, and this can lead
Cause the gathering in luminescent layer and electric transmission bed boundary for the hole of great quantities of spare.These factors all can lead to 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, greatly improve device
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 a class contains new main part, with four (4- trifluoromethyl -3- pyridine radicals) phosphine
Acid imide or four (4- trifluoromethyl -3,5- pyrimidine radicals) imines are complexes of red light iridium and its preparation side of 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 it includes four main parts and an assistant ligand；Described 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-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- trifluoros
Picoline -4-) any one in phthalazine derivatives；Described assistant ligand is four (4- trifluoromethyl -3- pyridine radicals) phosphono
Imines or four (4- trifluoromethyl -3,5- pyrimidine radicals) imines.
Preferably, in described main part and the pyridine derivate that is coordinated with carbon atom of iridium is：
Preferably, quinoline, isoquinolin, quinazoline and the phthalazine derivatives choosing being coordinated with nitrogen-atoms with iridium in described main part
From：In any one.
Preferably, described 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
With assistant ligand and sodium carbonate mixing；Described main part is 2- (4,6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- three
Fluoromethylpyridin -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 reacting by heating, response time 12-48h at 120-140 DEG C, is cooled to room temperature, vacuum distillation
Remove solvent, then with dichloromethane extraction, concentrate, through column chromatography for separation, obtain the crude product of coordination compound, obtain pure iridium through distillation
Coordination compound.
Preferably, the mol ratio of described 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 this complex of iridium of application, and it includes substrate, anode, hole transport
Layer, organic luminous layer, electron transfer layer and negative electrode；Described substrate is glass, and anode material is tin indium oxide (ITO)；Hole passes
Defeated layer uses 4,4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline (TAPC), electron transport layer materials use 3,3 '-
(5 '-(3- (pyridin-3-yl) phenyl)-[and 1,1 ': 3 ', 1 "-triphenyl] -3,3 "-diyl) two pyridines (TmPyPB), negative electrode employing
LiF/Al；Organic luminous layer adopts the double emitting layers of doped structure, material of main part is to use 4,4 ', 4 respectively "-three (carbazole -9- bases)
Triphenylamine (TcTa) and double (3- (9- carbazyl) phenyl) pyridine (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 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 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.
【Brief description】
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium RIr4-01 that the present invention provides；
Fig. 2 is used for the brightness-voltage curve of organic electroluminescence device for the complex of iridium RIr4-01 that the present invention provides；
Current efficiency-brightness that Fig. 3 is used for organic electroluminescence device for the complex of iridium RIr4-01 that the present invention provides is bent
Line.
【Specific embodiment】
The present invention is described in further detail with reference to the accompanying drawings and examples.The term being used in the present invention, unless
It is otherwise noted, typically there is the implication of those of ordinary skill in the art's generally reason.
The invention discloses a kind of complexes of red light iridium, it includes four new main parts and an assistant ligand.Institute
Stating assistant ligand is four (4- trifluoromethyl -3- pyridine radicals) imines or four (4- trifluoromethyl -3,5- pyrimidine radicals) phosphono Asia
Amine.Described main 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 pyridine -4-) isoquinolin, 2- (4,6- bis- fluoroforms
Yl pyridines -3-) quinazoline, 2- (4,6- bis- trifluoromethyl pyridine -4-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalein
Any one in piperazine, 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives.Joined with carbon atom with iridium in described main part
Position pyridine derivate be：Described quinoline, isoquinolin, quinazoline and phthalazine derivatives are selected from：In any one.Described assistant ligand is four (4- fluoroforms
Base -3- pyridine radicals) imines or four (4- trifluoromethyl -3,5- pyrimidine radicals) imines.
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, four (4- trifluoromethyl -3- pyridine radicals) imines or four (4- trifluoromethyl -
3,5- pyrimidine radicals) imines 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-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalein
Piperazine or 2- (4,6- bis- trifluoromethyl pyridine -4-) phthalazine derivatives are as the iridium dimerization bridging coordination compound of main part and assistant ligand
And sodium carbonate mixing；Add cellosolvo solution, carry out reacting by heating at 120-140 DEG C, response time 12-48h is cold
But to room temperature, vacuum distillation removes solvent, then with dichloromethane extraction, concentrates, through column chromatography for separation, obtain the thick of coordination compound
Product, obtain complex of iridium through sublimation purification.Wherein, described 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 described iridium dimerization bridging coordination compound, assistant ligand and sodium carbonate is 1: 2: 5.
Described complex of iridium has one of structure of following numbering RIr4-01～24：
Illustrate present invention below taking the complex of iridium as RIr4-01 for the numbering in wherein one embodiment as a example,
Will be helpful to further understand the present invention by following embodiments, but do not limit present disclosure.
The synthetic method of coordination compound RIr4-01
2- bromopyridine (26.39mmol), 4,6- bis- trifluoromethyl pyridine -3- boric acid (31.66mmol), four triphenyl phosphorus palladiums
(0.79mmol) it is dissolved in 100mL oxolane with sodium carbonate (60.00mmol), react 24 hours at 65 DEG C, cooling, plus
Enter water and dichloromethane, organic layer concentrates column chromatography and obtains main part (yield is 52.24%).By main part (13.08mmol)
It is dissolved in 15mL cellosolvo with iridous chloride (6.23mmol), 130 DEG C of reaction 12h of mixture, be subsequently adding auxiliary and join
Body (12.46mmol) and sodium carbonate (31.15mmol), continue 130 DEG C of reaction 24h.System cools down, and adds water and dichloromethane,
Organic layer concentrates column chromatography and obtains yellow solid RIr4-01, 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 four (4- fluoroforms
Base -3- pyridine radicals) imines or four (4- trifluoromethyl -3,5- pyrimidine radicals) imines are that auxiliary ligand design has synthesized one
Serial complexes of red light iridium.By designing part or complex structure, and repairing by simple chemical substituents on part
Decorations, reach the purpose that regulation and control coordination compound lights with electron mobility.
Described azacyclo- is all the group having stronger electron-transporting, is conducive to injection and the transmission of equilbrium carrier.
Described 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 below organic electroluminescence device being prepared as luminescent material using RIr4-01, 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 makes
With 4,4 '-cyclohexyl two, [N, N- bis- (4- aminomethyl phenyl) 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), thickness is 60nm, evaporation
Speed is 0.05nm/s；Negative electrode adopts LiF/A1.Organic luminous layer adopts the double emitting layers of doped structure, and it includes material of main part
And luminescent material, material of main part is to use 4,4 ', 4 respectively " double (3- (the 9- click of-three (carbazole -9- base) triphenylamines (TcTa) and 2,6-
Oxazolyl) phenyl) pyridine (26DCzPPy), selected luminescent material is described complex of iridium RIr4-01, and mass fraction is preferred
For 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.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 used for the photoelectric properties of organic electroluminescence device.As shown in Figures 2 and 3, described organic electroluminescent
The startup voltage of device is 3.5V, and its maximum power efficiency and current efficiency are respectively 60.05cd/A, high-high brightness 98532cd/
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 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 modifying to the chemical substituents of described part, invention achieves regulation and control cooperation
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 (7)
1. a kind of complex of iridium is it is characterised in that include four main parts and an assistant ligand；Described main part be 2- (4,
6- bis- trifluoromethyl pyridine -3-) quinoline, 2- (4,6- bis- trifluoromethyl pyridines _ 4-) quinoline, 2- (4,6- bis- trifluoromethyl pyridines -
3-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridines _ 4-) isoquinolin, 2- (4,6- bis- trifluoromethyl pyridine -3-) quinazoline, 2-
(4,6- bis- trifluoromethyl pyridines _ 4-) quinazoline and 2- (4,6- bis- trifluoromethyl pyridine -3-) phthalazines, 2- (4,6- bis- fluoroforms
Yl pyridines _ 4-) any one in phthalazine derivatives；Described assistant ligand is that four (4- trifluoromethyl -3- pyridine radicals) phosphono is sub-
Amine or four (4- trifluoromethyl -3,5- pyrimidine radicals) imines.
2. complex of iridium according to claim 1 is it is characterised in that in described main part and the pyrrole that is coordinated with carbon atom of iridium
Piperidine derivatives are：
3. complex of iridium according to claim 1 is it is characterised in that in described 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 is it is characterised in that described complex of iridium has one of following structure：
5. a kind of preparation method of the complex of iridium as described in any one as claim 1_4 is 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, described 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；Add cellosolvo solution, carry out reacting by heating, response time 12- at 120-140 DEG C
48h, is cooled to room temperature, and vacuum distillation removes solvent, then with dichloromethane extraction, concentrates, through column chromatography for separation, obtain coordination compound
Crude product, through distillation obtain pure complex of iridium.
6. complex of iridium according to claim 5 preparation method it is characterised in that described 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 as described in claim 1_4 any one for application is it is characterised in that wrap
Include substrate, anode, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode；Described substrate is glass, described anode
Material is tin indium oxide；Described hole transmission layer uses 4,4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline, described electricity
Sub- transport layer materials'use 3,3 '-(5 '-(3- (pyridin-3-yl) phenyl)-[1,1 '：3 ', 1 "-triphenyl] -3,3 "-diyl) two
Pyridine, negative electrode adopts LiF/Al；Organic luminous layer adopts the double emitting layers of doped structure, and material of main part is to use 4,4 ', 4 respectively "-
Three (carbazole -9- base) triphenylamines and double (3- (9- carbazyl) phenyl) pyridine of 2,6-；Selected luminescent material is that described iridium is joined
Compound, mass fraction 5wt%.
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| CN106957339A (en) * | 2017-04-21 | 2017-07-18 | 瑞声光电科技(常州)有限公司 | A kind of metal complex and its luminescent device |
| 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 |
| CN108997434A (en) * | 2018-05-28 | 2018-12-14 | 海南师范大学 | Complexes of red light iridium and its preparation method and application |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
|---|---|---|---|---|
| CN106957339A (en) * | 2017-04-21 | 2017-07-18 | 瑞声光电科技(常州)有限公司 | A kind of metal complex and its luminescent device |
| 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 |
| CN108997434A (en) * | 2018-05-28 | 2018-12-14 | 海南师范大学 | Complexes of red light iridium and its preparation method and application |
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