CN106117273A - The electroluminescent device of complex of iridium and its preparation method and application complex of iridium - Google Patents
The electroluminescent device of complex of iridium and its preparation method and application complex of iridium Download PDFInfo
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- CN106117273A CN106117273A CN201610466569.6A CN201610466569A CN106117273A CN 106117273 A CN106117273 A CN 106117273A CN 201610466569 A CN201610466569 A CN 201610466569A CN 106117273 A CN106117273 A CN 106117273A
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- iridium
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- pyridine
- piperazine
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 62
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 piperazine alkene 2 phenylpyridine derivative Chemical class 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 29
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000006471 dimerization reaction Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 claims description 6
- 150000003230 pyrimidines Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 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
- 239000010405 anode material Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 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
- 238000002156 mixing Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 4
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims 1
- 150000003053 piperidines Chemical class 0.000 claims 1
- 125000003386 piperidinyl group Chemical group 0.000 claims 1
- 238000005401 electroluminescence Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004020 luminiscence type 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
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 abstract 2
- 238000007385 chemical modification Methods 0.000 abstract 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 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
- 230000008020 evaporation Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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 2
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 1
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 1
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 1
- GYCPLYCTMDTEPU-UHFFFAOYSA-N 5-bromopyrimidine Chemical compound BrC1=CN=CN=C1 GYCPLYCTMDTEPU-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012141 concentrate Substances 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
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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
Abstract
The present invention relates to a class and have Novel main part, complex of iridium with acetylacetone,2,4-pentanedione as assistant ligand, the main part in this series complex of iridium molecule is containing chirality piperazine thiazolinyl group's (R) 4 piperazine alkene 2 phenylpyridine or (S) 4 piperazine alkene 2 phenylpyridine derivative.Compared to the complex of iridium being widely studied report, this kind of Novel iridium coordination compound that this invention is contained not only has beyond the advantages such as luminescence queenching effect little, stable chemical nature, the easy sublimation purification that luminous efficiency is high, cause due to concentration factor, and excellent device performance.By modify main part molecular structure, it is possible in visible wavelength range, regulate luminous intensity and the efficiency of coordination compound, this be display of organic electroluminescence and lighting source design production provide convenience.Meanwhile, the synthetic method of the series of new complex of iridium that the present invention introduces is simple, and productivity is higher, and the chemical modification for part is flexible.
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
The electroluminescent device of application 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 the key technology by dominating display in the future 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, 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 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.It 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 hole of great quantities of spare in luminescent layer and the gathering of electric transmission bed boundary.These factors all can cause the reduction of efficiency with tight
The efficiency roll-off of weight.Research shows, if complex of iridium has higher electron transport ability, it is possible to the effective electronics that increases exists
The transmission of luminescent layer and distribution, widen the region of 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.
[summary of the invention]
It is an object of the invention to provide the green glow iridium cooperation that a class contains Novel main part and acetylacetone,2,4-pentanedione assistant ligand
Thing and preparation method thereof, the high efficiency phosphorescent complex of iridium of preparation 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 two main parts and an acetylacetone,2,4-pentanedione assistant ligand, described master
Part be chirality piperazine thiazolinyl group (R-) 4-piperazine alkene-2-phenylpyridine or (S-) 4-piperazine alkene-2-phenylpyridine derivative in appoint
Meaning one, in described main part, and the pyridine derivate that iridium is coordinated with atom N isWith iridium with C Atomic coordinate
For benzene, naphthalene or pyridine, pyrimidine derivatives, and The position connected is 2, described benzene, naphthalene or pyridine, pyrimidine derivates
Any position of thing is replaced by halogen or alkyl, phenyl, pyridine radicals or pyrimidine radicals, and the quantity of described substituent group is 0-2.
Preferably, described halogen is F, and described alkyl is trifluoromethyl, and described phenyl is benzene, and described pyridine radicals is 3-pyridine
Any one of base, 4-fluoro-3-pyridine base, 4-trifluoromethyl-3-pyridine radicals or 4-piperazine annulated pyridine base, described pyrimidine radicals is 3,5-
Pyrimidine radicals or 4-trifluoromethyl-3, any one of 5-pyrimidine radicals.
Preferably, in described main part, and the pyridine derivate that iridium is coordinated with atom N isFormer with C with iridium
Son coordination for benzene, naphthalene or pyridine, pyrimidine derivatives, the position that both connect is 2, described benzene, naphthalene, pyridine and pyrimidine derivates
Thing is selected from:In substituted any one.
Preferably, described complex of iridium has one of following structure:
The present invention also provides for the preparation method of described complex of iridium: by the iridium dimerization bridging coordination compound containing two main parts
Mix with acetylacetone,2,4-pentanedione assistant ligand and sodium carbonate；Described main part is (R-) 4-piperazine alkene-2-phenyl pyrazoline of chirality piperazine thiazolinyl group
Any one in pyridine or (S-) 4-piperazine alkene-2-phenylpyridine derivative, adds cellosolvo solution, at 120-140 DEG C
Under carry out reacting by heating, response time 12-48h, be cooled to room temperature, decompression is distilled off solvent, then extracts with dichloromethane, dense
Contracting, through column chromatography for separation, obtains the crude product of coordination compound, obtains pure complex of iridium through distillation.
Preferably, the mol ratio of described iridium dimerization bridging coordination compound and acetylacetone,2,4-pentanedione, sodium carbonate is 1: 2: 5.
The present invention also provides for the electroluminescent device of a kind 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 indium stannum oxygen (ITO), hole transport
Layer uses 4, and [N, N-bis-(4-aminomethyl phenyl) aniline (TAPC), electron transfer layer uses 3,3 '-(5 '-(3-to 4 '-cyclohexyl two
(pyridin-3-yl) phenyl)-[1,1 ': 3 ', 1 "-triphenyl]-3,3 "-diyl) two pyridines (TmPyPB) material, 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, 4 "-three (carbazole-9-bases)
Triphenylamine (TcTa) and 2, double (3-(9-carbazyl) phenyl) pyridine (26DCzPPy) of 6-, selected luminescent material is MIr1-
01, mass fraction 5wt%.
Beneficial effects of the present invention: the complex of iridium that the present invention provides has luminous efficiency height, concentration quenching luminescent effect
Little and stable chemical nature, the feature of easy sublimation purification.The preparation method of described complex of iridium is simple, and productivity is higher, for organic
The design of electroluminescent display and lighting source produces and provides convenience.
[accompanying drawing explanation]
Fig. 1 is used for the electroluminescent spectrum of organic electroluminescence device for the complex of iridium MIr1-01 that the present invention provides；
Fig. 2 is used for the brightness-voltage curve of organic electroluminescence device for the complex of iridium MIr1-01 that the present invention provides；
The complex of iridium MIr1-01 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 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.
The complex of iridium of the present invention has all used iridous chloride, R/S-piperazine alkene, 1-Phenylethanone., 4-fluorophenethyl in building-up process
Ketone, 4-trifluoromethyl acetophenone, 4-phenyl acetophenone, 4-(3-pyridine radicals) 1-Phenylethanone., 4-(4-fluoro-3-pyridine base) 1-Phenylethanone.,
4-(4-trifluoromethyl-3-pyridine radicals) 1-Phenylethanone., 3-pyridine ethyl ketone, 4-pyridine ethyl ketone, 5-pyridine ethyl ketone, 2-acetonaphthone, 3-bromine
Pyridine, 5-Bromopyrimidine and acetylacetone,2,4-pentanedione etc., synthetic method is similar to.By the iridium dimerization bridging coordination compound containing two main parts and auxiliary
Help part acetylacetone,2,4-pentanedione and sodium carbonate mixing, described main part be chirality piperazine thiazolinyl group (R-) 4-piperazine alkene-2-phenylpyridine or
(S-) any one in 4-piperazine alkene-2-phenylpyridine derivative；Add cellosolvo solution, enter at 120-140 DEG C
Row reacting by heating, response time 12-48h, it is cooled to room temperature, decompression is distilled off solvent, then extracts with dichloromethane, concentrates,
Through column chromatography for separation, obtain the crude product of coordination compound, obtain pure complex of iridium through distillation.
Wherein, described iridium dimerization bridging coordination compound contains two main parts, and described main part is chirality piperazine thiazolinyl group
(R-) any one in 4-piperazine alkene-2-phenylpyridine or (S-) 4-piperazine alkene-2-phenylpyridine derivative, described iridium dimerization bridging
The mol ratio of coordination compound, assistant ligand 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 coordination compound MIr1-01, illustrate present invention, by following embodiment
Will assist in and be further appreciated by the present invention, but be not intended to present disclosure.
The synthetic method of coordination compound MIr1-01
The synthesis of complex of iridium is as follows: by (R-) 4-piperazine alkene-2-phenylpyridine (13.08mmol) and iridous chloride
(6.23mmol) it is dissolved in 15mL cellosolvo, 130 DEG C of mixture reaction 12h, is subsequently adding acetylacetone,2,4-pentanedione
(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 MIr1-01, and sublimation purification obtains the sterling (productivity is 45%) of coordination compound.
MS (ESI): calcd.for M+(C41H43IrN2O2 +) m/z=788.01, found 788.05.Anal.Calcd
for C41H44IrN4O2(789.0173): C 62.41, H 5.62, N 3.55.Found:C 62.38, H 5.59, N 3.58.
The present invention is with (R-) 4-piperazine alkene-2-phenylpyridine rolled into a ball containing chirality piperazine thiazolinyl or (S-) 4-piperazine alkene-2-phenyl pyrazoline
Piperidine derivatives is as main part, and with acetylacetone,2,4-pentanedione as assistant ligand, design has synthesized the iridium of a series of different glow color and coordinated
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 piperazine alkene is bigger sterically hindered owing to having, and decreases the concentration quenching luminescent effect of coordination compound, is conducive to
The raising of device performance.
Described complex of iridium has higher luminous efficiency, and after optimized checking, its preparation method is simple, and productivity is relatively
High.
The preparation of organic electroluminescence device
As a example by preparing organic electroluminescence device using MIr1-01 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 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-(pyridine-
3-yl) phenyl)-[1,1 ': 3 ', 1 "-triphenyl]-3,3 "-diyl) two pyridines (TmPyPB), thickness is 60nm, and evaporation rate is
0.05nm/s；Negative electrode use LiF/Al, LiF thickness be 1nm, evaporation rate be 0.01nm/s, Al thickness be 100nm, evaporation speed
Rate is 0.2nm/s.Organic luminous layer uses the double emitting layers of doped structure, and every layer thickness is 12nm, 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 MIr1-01, mass fraction 5wt%.
The different materials structure preparing device in the present invention is as follows:
The present invention selects a kind of green glow 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 provided 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 3.2V, and its maximum power efficiency and current efficiency are respectively 88.29lm/W and 103.50cd/A, maximum
Brightness 135676cd/m2.By research photophysical property, show that this kind of phosphorescent iridium complex has higher device efficiency,
The fields such as display and illumination have 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, it is also possible to make improvement, but these belong to the protection model of the present invention
Enclose.
Claims (7)
1. a complex of iridium, it is characterised in that it contains two main parts and an acetylacetone,2,4-pentanedione assistant ligand, and described master joins
Body be chirality piperazine thiazolinyl group (R-) 4-piperazine alkene-2-phenylpyridine or (S-) 4-piperazine alkene-2-phenylpyridine derivative in any
One, in described main part, and the pyridine derivate that iridium is coordinated with atom N isWith iridium with C Atomic coordinate it is
Benzene, naphthalene or pyridine, pyrimidine derivatives, andThe position connected is 2, described benzene, naphthalene or pyridine, pyrimidine derivatives
Any position replaced by halogen or alkyl, phenyl, pyridine radicals or pyrimidine radicals, the quantity of described substituent group is 0-2.
Complex of iridium the most according to claim 1, it is characterised in that described halogen is F, described alkyl is trifluoromethyl,
Described phenyl is benzene, and described pyridine radicals is 3-pyridine radicals, 4-fluoro-3-pyridine base, 4-trifluoromethyl-3-pyridine radicals or 4-piperazine alkene pyrrole
Any one of piperidinyl, described pyrimidine radicals is 3,5-pyrimidine radicals or 4-trifluoromethyl-3, any one of 5-pyrimidine radicals.
Complex of iridium the most according to claim 2, it is characterised in that in described main part, and the pyrrole that iridium is coordinated with atom N
Piperidine derivatives isWith iridium with C Atomic coordinate as benzene, naphthalene or pyridine, pyrimidine derivatives, the position that both connect
Being 2, described benzene, naphthalene, pyridine and pyrimidine derivatives are selected from:In substituted arbitrarily
A kind of.
Complex of iridium the most according to claim 3, it is characterised in that described complex of iridium has one of following structure:
5. the preparation method of a complex of iridium, it is characterised in that by the iridium dimerization bridging coordination compound containing two main parts and
Acetylacetone,2,4-pentanedione assistant ligand and sodium carbonate mixing；Described main part is (R-) 4-piperazine alkene-2-phenylpyridine of chirality piperazine thiazolinyl group
Or any one in (S-) 4-piperazine alkene-2-phenylpyridine derivative, add cellosolvo solution, at 120-140 DEG C
Carrying out reacting by heating, response time 12-48h, be cooled to room temperature, decompression is distilled off solvent, then extracts with dichloromethane, dense
Contracting, through column chromatography for separation, obtains the crude product of coordination compound, obtains pure complex of iridium through distillation.
The preparation method of complex of iridium the most according to claim 5, it is characterised in that described iridium dimerization bridging coordination compound and
Acetylacetone,2,4-pentanedione, the mol ratio of sodium carbonate are 1: 2: 5.
7. application as described in any one of claim 1-4 an electroluminescent device for complex of iridium, it include substrate, anode,
Hole transmission layer, organic luminous layer, electron transfer layer and negative electrode, described 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 transfer layer uses 3,3 '-
(5 '-(3-(pyridin-3-yl) phenyl)-[and 1,1 ': 3 ', 1 "-triphenyl]-3,3 "-diyl) two pyridines (TmPyPB) material, negative electrode
Using 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-yl) triphenylamine (TcTa) and 2, double (3-(9-carbazyl) phenyl) pyridine (26DCzPPy) of 6-, selected luminescent material is
MIr1-01, mass fraction 5wt%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070278936A1 (en) * | 2006-06-02 | 2007-12-06 | Norman Herron | Red emitter complexes of IR(III) and devices made with such compounds |
| CN102339339A (en) * | 2010-07-23 | 2012-02-01 | 中国石油化工股份有限公司 | Method for analyzing remaining oil distribution of fractured-vuggy reservoir |
-
2016
- 2016-06-23 CN CN201610466569.6A patent/CN106117273A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070278936A1 (en) * | 2006-06-02 | 2007-12-06 | Norman Herron | Red emitter complexes of IR(III) and devices made with such compounds |
| CN102339339A (en) * | 2010-07-23 | 2012-02-01 | 中国石油化工股份有限公司 | Method for analyzing remaining oil distribution of fractured-vuggy reservoir |
Non-Patent Citations (1)
| Title |
|---|
| HONG ZHI XIE等，: "Reduction of Self-Quenching Effect in Organic Electrophosphorescence Emitting Devices via the Use of Sterically Hindered Spacers in Phosphorescence Molecules", 《ADV. MATER.》 * |
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