CN105669767A - Iridium complex and preparation method thereof and luminous device using iridium complex - Google Patents
Iridium complex and preparation method thereof and luminous device using iridium complex Download PDFInfo
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- CN105669767A CN105669767A CN201610126161.4A CN201610126161A CN105669767A CN 105669767 A CN105669767 A CN 105669767A CN 201610126161 A CN201610126161 A CN 201610126161A CN 105669767 A CN105669767 A CN 105669767A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 53
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000010668 complexation reaction Methods 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 11
- -1 phosphoryl structure Chemical group 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000000859 sublimation Methods 0.000 claims abstract description 5
- 230000008022 sublimation Effects 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 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 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000006471 dimerization reaction Methods 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- 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 claims description 3
- 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 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 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
- WLAKUAILRGATSL-UHFFFAOYSA-N 2,4-difluoropyridine Chemical class FC1=CC=NC(F)=C1 WLAKUAILRGATSL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002503 iridium Chemical class 0.000 abstract 3
- 238000007385 chemical modification Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 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
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- LUGGQBCOTDQVME-OUPQRBNQSA-N C=C/C=C\C=C/N Chemical compound C=C/C=C\C=C/N LUGGQBCOTDQVME-OUPQRBNQSA-N 0.000 description 1
- YDIGMBAPTZJCKF-UHFFFAOYSA-O C[NH2+]CN=CN=C Chemical compound C[NH2+]CN=CN=C YDIGMBAPTZJCKF-UHFFFAOYSA-O 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- HOJLDGRYURJOJS-UHFFFAOYSA-N phosphoric acid;pyridine Chemical compound OP(O)(O)=O.C1=CC=NC=C1 HOJLDGRYURJOJS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 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
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- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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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)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an iridium complex with a novel coordination mode and taking nitrogen heterocyclic ring phosphoric acid as an auxiliary ligand. The series of iridium complexes contains two 2,4-difluoropyridine dipyridyl derivatives serving as main ligands and an auxiliary main ligand with a nitrogen heterocyclic ring phosphoric acid structure. Compared with the widely studied and reported iridium complexes, the novel iridium complex provided by the invention has the advantages of high luminous efficiency, stable chemical properties, easiness in sublimation and purification and the like; and moreover, due to the introduction of a strong-ligand field phosphoryl structure, the emitting color of the complex can be effectively controlled. By modifying the molecular structures of the main ligand and auxiliary ligand, the light emitting position of the complex can be adjusted within the wavelength range of blue light, thereby facilitating the design and production of organic electroluminescence displays and lighting sources. Meanwhile, according to the series of novel iridium complexes provided by the invention, the synthesis method is simple, the yield is relatively high, and the chemical modification of the main ligand and auxiliary ligand is flexible.
Description
[technical field]
The present invention relates to organic electroluminescence device technical field, particularly relate to the luminescent device of a class complex of iridium and its preparation method and application 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 in succession based on high-tech energy sustainability technology and industry. Organic electroluminescence device (OLEDs) is because its visual angle is wide, brightness is high, energy consumption is low and can prepare the plurality of advantages such as flexible device, and receives much attention, and is referred to as the key technology by dominating display in the future world. In recent years, big quantity research shows, in numerous heavy metal element coordination compounds, complex of iridium is considered as the most ideal chose of OLEDs phosphor material. There is 5d76s2The iridium atom of outer electronic structure, after forming+3 valency cationes, has 5d6Electron configuration, has stable hexa-coordinate octahedral structure, makes material have higher chemical stability and heat stability. Meanwhile, Ir (III) has bigger spin orbit coupling constant (ξ=3909cm-1), be conducive to improving the interior quantum yield of coordination compound and reducing luminescent lifetime, thus improving the overall performance of luminescent device.
Compared to HONGGUANG and green glow complex of iridium, the energy of blue emission is of a relatively high, and this just requires that blue phosphorescent complex of iridium has higher T1 energy level and wider HOMO/LUMO energy level difference. Research shows, rising along with triplet, the speed of radiation transistion and nonradiative transition all can increase, and the increase amplitude of the latter often becomes apparent from, cause that luminous efficiency declines, therefore, launch the blue shift of wavelength and high internal quantum efficiency be contradictory relation, this just exploitation to blue light compound add difficulty. It addition, have the blue light compound of relatively bob ejected wave length, its luminous efficiency is all relatively low.
Therefore, it is necessary to provide the complex of iridium that a kind of luminous efficiency is high.
[summary of the invention]
It is an object of the invention to provide blue light and the luminous complex of iridium of other different colours and preparation method thereof that a class is assistant ligand with azacyclo-phosphoric acid, azacyclo-phosphoric acid can prepare efficient phosphorescent iridium complex as assistant ligand, such coordination compound as the centre of luminescence, can be applied in organic electroluminescence device.
The present invention provides a kind of complex of iridium, it is characterised in that it includes one and connects the main part of pyridine derivate and the assistant ligand of a nitrogen heterocyclic ring phosphoric acid containing two 2,4-difluoro pyridines, and the pyridine derivate in described main part is:Wherein, R1For any one in alkyl, nitrogen substituent group or aryl;Described phenyl, pyridine radicals any position replaced by the haloalkyl of halogen and/or C1-C6, on described phenyl, the quantity of substituent group is 0-4; On described pyridine radicals, the quantity of substituent group is 0-3, and wherein, nitrogen heterocyclic ring phosphoric acid isWherein, azacyclo-For any one in substituted or non-substituted pyridine radicals, pyrimidine radicals or triazine radical, R2For substituted or non-substituted phenyl, any one in naphthyl, pyridine radicals, pyrimidine radicals or triazine radical, described phenyl, any position of naphthyl, pyridine radicals or pyrimidine radicals is replaced by the haloalkyl of halogen and/or C1-C6, and on described phenyl, the quantity of substituent group is 0-4; On described pyridine radicals, the quantity of substituent group is 0-3, and on described naphthyl, the quantity of substituent group is 0-6, and on described pyrimidine radicals, substituent group quantity is 0-2.
Preferably, described halogen is any one in F, Cl, Br, I, and described haloalkyl is the haloalkyl of the C1-C6 of single halogen substiuted or multiple identical or different halogen substiuted.
Preferably, described nitrogen heterocyclic ring is selected from:OrIn any one; Described R2It is selected fromOrIn any one.
Preferably, described complex of iridium one of is structured with:
The preparation method that the present invention also provides for described complex of iridium: coordination compound and nitrogen heterocyclic ring phosphoric acid and sodium carbonate mixing will be connected as the iridium dimerization bridge of part containing pyridine derivate; Add cellosolvo solution, reaction it is heated at 100 DEG C-150 DEG C, response time 24h-48h, being cooled to room temperature, decompression is distilled off solvent, with dichloromethane extraction, concentration, through column chromatography for separation, obtaining the complex of iridium crude product being assistant ligand with nitrogen heterocyclic ring phosphoric acid, coordination compound obtains complex of iridium through sublimation purification.
Preferably, described iridium dimerization bridge connects coordination compound and contains pyridine derivate, and the mol ratio that described iridium dimerization bridge connects coordination compound, azacyclo-phosphoric acid and sodium carbonate is 1:2:5. The present invention also provides for the luminescent device of a kind of this complex of iridium of application, it includes substrate, anode, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode, and described substrate is glass, and anode is indium stannum oxygen, cavitation layer adopts TAPC material, and electron transfer layer adopts TmPyPB material to prepare.
Beneficial effects of the present invention: complex of iridium provided by the invention has the feature of luminous efficiency height, stable chemical nature, easy sublimation purification. The preparation method of described complex of iridium is simple, and productivity is higher. Due to the introducing of phosphorus oxygen key of polarization, the glow color of coordination compound and improve electronic transmission performance can Effective Regulation; By modifying the molecular structure of main part and assistant ligand, it is possible to regulate the luminous position of coordination compound in all visible wavelength ranges, the design production for display of organic electroluminescence and lighting source is provided convenience.
[accompanying drawing explanation]
Fig. 1 is the complex of iridium BBIr2-001 provided by the invention electroluminescent spectrum for organic electroluminescence device;
Fig. 2 is the complex of iridium BBIr2-001 provided by the invention photoelectric properties for organic electroluminescence device;
Fig. 3 is the complex of iridium BBIr2-001 provided by the invention photoelectric properties for organic electroluminescence device;
Fig. 4 is the complex of iridium BBIr2-001 provided by the invention photoelectric properties for organic electroluminescence device.
[detailed description of the invention]
Below in conjunction with drawings and Examples, the present invention is described in further detail. The term used in the present invention, except as otherwise noted, generally has the implication that those of ordinary skill in the art generally manage.
The complex of iridium of the present invention has all used iridous chloride, 2-bromopyridine, 2,4-difluoro pyridine boric acid etc. in building-up process, and synthetic method is similar.Coordination compound and nitrogen heterocyclic ring phosphoric acid and sodium carbonate mixing will be connected as the iridium dimerization bridge of part containing pyridine derivate; Add cellosolvo solution, reaction it is heated at 100 DEG C-150 DEG C, response time 24h-48h, being cooled to room temperature, decompression is distilled off solvent, then with dichloromethane extraction, concentration, through column chromatography for separation, obtain the crude product being assistant ligand with nitrogen heterocyclic ring phosphoric acid, obtain complex of iridium through sublimation purification. Wherein, described iridium dimerization bridge connects coordination compound and contains pyridine derivate, and the mol ratio that described iridium dimerization bridge connects coordination compound, azacyclo-phosphoric acid and sodium carbonate is 1:2:5.
Below with a wherein embodiment, complex B BIr2-001 is that example illustrates present invention, be will assist in by following embodiment and is further appreciated by the present invention, but is not intended to present disclosure.
The synthetic method of complex B BIr2-001
2-bromopyridine (4.17g, 26.39mmol), 2,4-difluoro pyridine boric acid (5.04g, 31.67mmol), four triphenyl phosphorus palladium (0.91g, 0.79mmol) and sodium carbonate (6.36g, 60.00mmol) be dissolved in 100mL oxolane, 65 DEG C are reacted 24 hours, and cooling adds water and dichloromethane, organic layer evaporating column chromatography obtains main part (3.86g, productivity 76.19%). By main part (2.51g, 13.08mmol) and iridous chloride (2.30g, 6.23mmol) it is dissolved in 15mL2-ethoxy ethanol, 135 DEG C of mixture reaction 12h, it is subsequently adding pyridine phosphoric acid (2.72g, 12.47mmol) and sodium carbonate (3.30g, 31.15mmol), continue 140 DEG C of reaction 30h. System cools down, and adds water and dichloromethane, and organic layer evaporating column chromatography obtains yellow solid BBIr2-001 (1.16g, productivity: 23.5%).
1HNMR(400MHz,CDCl3, δ): 9.67 (d, J=5.5Hz, 1H), 8.38 (d, J=8.8Hz, 1H), 8.23 (d, J=8.4Hz, 1H), 7.81 7.73 (m, 4H), 7.42 7.32 (m, 5H), 7.23 (dd, J=7.2,5.7Hz, 1H), 7.15 (td, J=7.5,3.0Hz, 2H), 6.79 (t, J=6.2Hz, 1H), 6.53 6.39 (m, 2H), 5.76 (dd, J=8.8,2.2Hz, 1H), 5.61 (dd, J=8.7,2.2Hz, 1H).31PNMR(400MHz,CDCl3,δ):34.31ppm(s).EI,[M]calcdforC33H21F4IrN3O2P, 793.08; Found793.10
The present invention is with azacyclo-phosphoric acid for assistant ligand, and design has synthesized a series of blue light and the complex of iridium of other different colours luminescence. By designing part or complex structure, and by the modification of simple chemical substituents on part, reach the purpose of regulation and control coordination compound glow color.
The phosphorus oxygen key of described azacyclo-phosphoric acid and azacyclo-are all the groups having stronger electron-transporting, effectively in the injection of equilbrium carrier and transmission, improve luminous efficiency.
Described complex of iridium has higher interior quantum yield, and after optimized checking, its preparation method is simple, and productivity is higher.
The preparation of organic electroluminescence device
Prepare organic electroluminescence device for BBIr2-001 as luminescent material below, the preparation of organic electroluminescence device of the present invention is described. .
OLEDs device includes: substrate, anode, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode.
In the element manufacturing of the present invention, substrate is glass, and anode material is indium stannum oxygen (ITO); Hole transmission layer uses 4,4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline (TAPC), electron transport layer materials uses 3,3'-(5'-(3-(pyridin-3-yl) phenyl)-[1,1':3'; 1 "-triphenyl]-3; 3 "-two bases) two pyridines (TmPyPB), thickness is 60nm, and evaporation rate is 0.05nm/s;Negative electrode adopts LiF/Al, LiF thickness to be 1nm, and evaporation rate is 0.01nm/s, Al thickness is 100nm, and evaporation rate is 0.2nm/s. Organic luminous layer adopts doped structure, and material of main part is with 1,3-bis-(9H-carbazole-9-base) benzene (mCP), and selected luminescent material is BBIr2-001. Thickness is 40nm, and evaporation rate is 0.05nm/s, BBIr2-001 mass fraction 8%.
Different materials structure in the present invention is as follows:
The present invention selects a kind of blue light complex preparation organic electroluminescence device. See also Fig. 1, Fig. 2, Fig. 3 and Fig. 4, Fig. 1 is the complex of iridium provided by the invention electroluminescent spectrum for organic electroluminescence device, Fig. 2 is the complex of iridium provided by the invention photoelectric properties for organic electroluminescence device, Fig. 3 is the complex of iridium provided by the invention photoelectric properties for organic electroluminescence device, and Fig. 4 is the complex of iridium provided by the invention photoelectric properties for organic electroluminescence device. As shown in figs 2-4, when the startup voltage of described organic electroluminescence device is 3.5V, its maximum power efficiency, current efficiency and external quantum efficiency respectively 34.20lm/W, 43.50cd/A and 19.1%. During the applied voltage 10.0V of organic electroluminescence device, it reaches high-high brightness 26152cd/m2. By studying photophysical property, it was shown that the phosphorescent iridium complex of this kind of assistant ligand containing azacyclo-phosphorus oxygen structure has higher luminous efficiency.
Therefore, utilize azacyclo-phosphoric acid as the second cyclic metal complexes can the coordination compound of effectively synthesizing high lumineseent performance, different colours, and show good device performance, it was shown that this kind of material has actual application value in fields such as display and illuminations.
Such phosphor material provided by the invention can be applied to the emission layer of phosphorescent OLED s as the centre of luminescence, by designing part or complex structure, and by the chemical substituents of described part is modified, invention achieves the purpose of regulation and control coordination compound glow color.
Above-described is only embodiments of the present invention, it should be noted here that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, it is also possible to make improvement, but these belong to protection scope of the present invention.
Claims (7)
1. a complex of iridium, it is characterised in that it includes and connects the main part of pyridine derivate and the assistant ligand of a nitrogen heterocyclic ring phosphoric acid containing two 2,4-difluoro pyridines, and the pyridine derivate in described main part is:Wherein, R1For any one in alkyl, nitrogen substituent group or aryl; Described phenyl, pyridine radicals any position replaced by the haloalkyl of halogen and/or C1-C6, on described phenyl, the quantity of substituent group is 0-4; On described pyridine radicals, the quantity of substituent group is 0-3, and wherein, nitrogen heterocyclic ring phosphoric acid isAzacyclo-For any one in substituted or non-substituted pyridine radicals, pyrimidine radicals or triazine radical, R2For substituted or non-substituted phenyl, any one in naphthyl, pyridine radicals, pyrimidine radicals or triazine radical, described phenyl, any position of naphthyl, pyridine radicals or pyrimidine radicals is replaced by the haloalkyl of halogen and/or C1-C6, and on described phenyl, the quantity of substituent group is 0-4; On described pyridine radicals, the quantity of substituent group is 0-3, and on described naphthyl, the quantity of substituent group is 0-6, and on described pyrimidine radicals, substituent group quantity is 0-2.
2. complex of iridium according to claim 1, it is characterised in that described halogen be in F, Cl, Br, I any one or multiple, described haloalkyl is the haloalkyl of the C1-C6 of single halogen substiuted or multiple halogen substiuted.
3. complex of iridium according to claim 2, it is characterised in that described azacyclo-is selected from:In any one; Described R2It is selected fromIn any one.
4. complex of iridium according to claim 3, it is characterised in that described complex of iridium one of is structured with:
5. the preparation method of a complex of iridium, it is characterised in that coordination compound and nitrogen heterocyclic ring phosphoric acid and sodium carbonate mixing will be connected as the iridium dimerization bridge of part containing pyridine derivate; Add cellosolvo solution, reaction it is heated at 100 DEG C-150 DEG C, response time 24h-48h, being cooled to room temperature, decompression is distilled off solvent, then with dichloromethane extraction, concentration, through column chromatography for separation, obtain the crude product being assistant ligand with nitrogen heterocyclic ring phosphoric acid, obtain complex of iridium through sublimation purification.
6. the preparation method of complex of iridium according to claim 5, it is characterised in that the mol ratio that described iridium dimerization bridge connects coordination compound, azacyclo-phosphoric acid and sodium carbonate is 1:2:5.
7. application luminescent device of complex of iridium as described in claim 1-4, it includes substrate, anode, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode, described substrate is glass, anode is indium stannum oxygen, cavitation layer adopts TAPC material, and electron transfer layer adopts TmPyPB material to prepare.
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