CN107522745A - A kind of preparation method and application using azacyclo- sulfonic acid as the complex of iridium of the second main part - Google Patents
A kind of preparation method and application using azacyclo- sulfonic acid as the complex of iridium of the second main part Download PDFInfo
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- CN107522745A CN107522745A CN201610439463.7A CN201610439463A CN107522745A CN 107522745 A CN107522745 A CN 107522745A CN 201610439463 A CN201610439463 A CN 201610439463A CN 107522745 A CN107522745 A CN 107522745A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 95
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 claims abstract description 10
- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 27
- 125000001188 haloalkyl group Chemical group 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract 3
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 125000001475 halogen functional group Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 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 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 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 2
- QQLRSCZSKQTFGY-UHFFFAOYSA-N (2,4-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(F)C=C1F QQLRSCZSKQTFGY-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- -1 3- (pyridine-3-yl) phenyl Chemical group 0.000 description 1
- YWKKLBATUCJUHI-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C)=CC=1)C1=CC=CC=C1 YWKKLBATUCJUHI-UHFFFAOYSA-N 0.000 description 1
- MZYDBGLUVPLRKR-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 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
- 239000012043 crude product Substances 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000012044 organic layer Substances 0.000 description 1
- 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 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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 discloses a kind of complex of iridium, structural formula such as formula (1), formula (2) or the formula (3) of the complex of iridium are shown： Wherein, Ar1Selected from following at least one：Substituted or non-substituted pyridine radicals, substituted or non-substituted pyrazolyl, substituted or non-substituted indazolyl, Ar2Selected from following at least one：Substituted or non-substituted aromatic ring, substituted or non-substituted heteroaromatic, Ar3Selected from following at least one：Substituted or non-substituted nitrogen heterocyclic ring.The invention also discloses the application in organic electroluminescence device is prepared of the preparation method of complex of iridium, complex of iridium and organic electroluminescence device.Complex of iridium of the present invention can be used as the centre of luminescence, can be applied to prepare organic electroluminescence device.The preparation method of the complex of iridium of the present invention is simple.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an iridium complex, a preparation method and application thereof and an organic electroluminescent device.
Background
Under the large background of increasing global energy demand and great ecological environment worries, governments of various countries continuously and vigorously develop sustainable energy-saving technologies and industries based on high technology. Organic electroluminescent devices (OLEDs) are attracting attention due to their advantages of wide viewing angle, high brightness, low power consumption, and the ability to fabricate flexible devices, and are known as key technologies that will dominate the future display world. Therefore, governments and enterprises of various countries have spread the OLEDs industry, for example: kodak in the united states, UDC, philips in the netherlands, siemens in germany, sony in japan, samsung in korea, LG, and the like.
In 1997, electro-phosphorescence was reported almost simultaneously by horses in light and Forrest et al, who used Os (II) diimine complex Os (CN)2(PPh3)2X and platinum octaethylporphyrin PtOEP are used as phosphorescent materials, and the single-triplet and triplet excited state energy is utilized simultaneously, so that the efficiency of the prepared device is greatly superior to that of the previous fluorescent materials [ (a) Y.G.Ma, H.Y.Zhang, J.C.Shen, C.M.Che, Synth.Met.1998, 94 and 245; (b) m.a.baldo, d.f.o' Brien, y.you, a.shoustikov, s.sibley, m.e.thompson, s.r.forrest, Nature 1998, 395, 151.]. The research on efficient phosphorescent organic electroluminescent devices (PhOLEDs) has thus far raised a new trend of organic electroluminescent research. In recent years, a great deal of research has shown that, among numerous heavy metal element complexes, iridium complexes are considered to be the most desirable choice for OLEDs phosphorescent materials. Having a 5d76s2The iridium atom of the outer shell electronic structure has a valence of 5d after forming a +3 cation6Electronic configuration, with stable hexa-coordinated octahedral structure, makes the material have higher chemical stability and thermal stability, meanwhile, Ir (III) has larger spin-orbit coupling constant (ξ ═ 3909 cm)-1) Is favorable for improving the internal quantum yield of the complex and reducing the luminescence life, thereby improvingThe overall performance of the light emitting device. The primary colors of red, green and blue are of great importance as efficient display and illumination devices.
Disclosure of Invention
The invention aims to provide an iridium complex which can be used as a luminescence center.
The invention also aims to provide a preparation method of the iridium complex, and the prepared iridium complex can be used as a luminescence center.
The invention also aims to provide application of the iridium complex in preparing an organic electroluminescent device, and the organic electroluminescent device can be prepared by taking the iridium complex as a luminescence center.
It is still another object of the present invention to provide an organic electroluminescent device using an iridium complex as a luminescence center.
The technical scheme of the invention is as follows:
an iridium complex, the structural formula of which is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
A method of preparing an iridium complex, comprising: mixing the iridium dimeric bridged complex, azacyclo sulfonic acid and potassium carbonate, and adding 2-ethoxyethaneAn alcohol solution is used for obtaining a first solution, wherein the iridium dimeric bridged complex is provided with an aromatic ring-linked azacyclo serving as a first main ligand, and the second main ligand is azacyclo sulfonic acid; heating the first solution for reaction, and cooling to obtain a second solution; removing the solvent of the second solution, and extracting to obtain an organic phase; separating the organic phase by column chromatography to obtain a compound with a structural formula shown in formula (1), formula (2) or formula (3): wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
Use of an iridium complex as described above in the preparation of an organic electroluminescent device.
And, an organic electroluminescent device comprising: the organic electroluminescent device comprises a substrate, an anode, a hole transport layer, an organic electroluminescent layer, an electron transport layer and a cathode which are sequentially stacked, wherein the organic electroluminescent layer is made of an iridium complex, and the structural formula of the iridium complex is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
Compared with the prior art, the invention has the following advantages:
1. the iridium complex has a structure with azacyclo-sulfonic acid as a second main ligand, and the azacyclo-sulfonic acid structure can be used as an auxiliary ligand to prepare a high-efficiency phosphorescent iridium complex, so that the complex can be used as a luminescence center.
2. The iridium complex has a structure with azacyclo-sulfonic acid as a second main ligand, and due to the introduction of polarized sulfur-oxygen bonds into the structure, the sulfur-oxygen bonds and the azacyclo are good electron transmission groups, so that the injection and transmission of balanced carriers are facilitated, the luminescent color of the iridium complex can be effectively regulated, the electron transmission performance is improved, and the luminescent efficiency is improved.
3. According to the iridium complex, the molecular structures of the aromatic ring-linked nitrogen heterocycle serving as the first main ligand and the nitrogen heterocycle sulfonic acid serving as the second main ligand are modified in a substitution mode, so that the light-emitting position of the iridium complex can be adjusted in all visible light wavelength ranges, and the purpose of regulating and controlling the light-emitting color of the iridium complex is achieved.
4. The iridium complex of the invention has blue light emission and different color light emission, and has higher internal quantum yield.
5. The iridium complex also has the advantages of stable chemical property, easy sublimation and purification and the like.
6. The iridium complex has the advantages of simple preparation method and high yield, and is flexible in chemical modification of aromatic ring linked nitrogen heterocycles serving as a first main ligand and nitrogen heterocyclic sulfonic acid serving as a second main ligand.
7. The iridium complex can be applied to an organic electroluminescent device, and can obtain good device brightness and efficiency, thereby providing convenience for the design and production of an organic electroluminescent display and an illumination light source.
8. The iridium complex is used as a phosphorescent material in the organic electroluminescent device, and is applied to an organic electroluminescent layer, so that the organic electroluminescent device has good device brightness and efficiency.
Drawings
FIG. 1 is a graph of the UV-VIS absorption spectrum and photoluminescence spectrum of an iridium complex of example 1;
FIG. 2 is the electroluminescence spectrum of the OLED device of example 2;
FIG. 3 is a graph of current efficiency as a function of current density for the OLED device of example 2;
FIG. 4 is a graph of power efficiency as a function of current density for the OLED device of example 2;
fig. 5 is a graph of current density and luminance versus voltage for the OLED device of example 2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in further detail below.
The invention discloses an iridium complex. The structural formula of the iridium complex is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting ofThe method comprises the following steps: substituted or unsubstituted nitrogen-containing heterocycles.
As shown in the formulas (1) to (3), the iridium complex has a structure with azacyclo-sulfonic acid as a second main ligand, and the azacyclo-sulfonic acid structure can be used as an auxiliary ligand to prepare a high-efficiency phosphorescent iridium complex, so that the complex can be used as a luminescence center. In addition, because the nitrogen heterocyclic sulfonic acid structure introduces polarized sulfur-oxygen bonds, the sulfur-oxygen bonds and the nitrogen heterocyclic rings (including aromatic ring linked nitrogen heterocyclic rings serving as a first main ligand) are good electron transmission groups, so that the injection and transmission of balanced carriers are facilitated, the luminescent color of the iridium complex can be effectively regulated and controlled, the electron transmission performance is improved, and the luminescent efficiency is improved.
Preferably, the iridium complex can adjust the luminescent position of the iridium complex in all visible light wavelength ranges by adopting a simple chemical substituent modification mode on the structures of the aromatic ring-linked nitrogen heterocycle serving as the first main ligand and the nitrogen heterocycle sulfonic acid serving as the second main ligand, so that the purpose of regulating the luminescent color of the iridium complex is achieved.
Preferably, Ar is2At least one selected from the group consisting of: substituted or unsubstituted benzene ring, substituted or unsubstituted pyridine ring.
Preferably, Ar is3At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted imidazolyl.
In a preferred embodiment of the present invention, the iridium complex has a structural formula as shown in any one of formulas (4) to (15):
wherein,R1～R13each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy. More preferably, the halogen is selected from at least one of the following: F. cl, Br and I. More preferably, the haloalkyl group is selected from at least one of: a single halo-substituted alkyl group, at least two same halo-substituted alkyl groups, at least two different halo-substituted alkyl groups, the halo in the haloalkane being selected from at least one of: F. cl, Br and I.
In another preferred embodiment of the present invention, the iridium complex has a structural formula as shown in any one of formulas (16) to (27):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy. More preferably, the halogen is selected from at least one of the following: F. cl, Br and I. More preferably, the haloalkyl group is selected from at least one of: a single halo-substituted alkyl group, at least two same halo-substituted alkyl groups, at least two different halo-substituted alkyl groups, the halo in the haloalkane being selected from at least one of: F. cl, Br and I.
In still another preferred embodiment of the present invention, the iridium complex has a structural formula as shown in formulas (28) to (39):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy. More preferably, the halogen is selected from at least one of the following: F. cl, Br and I. More preferably, the haloalkyl group is selected from at least one of: a single halo-substituted alkyl group, at least two same halo-substituted alkyl groups, at least two different halo-substituted alkyl groups, the halo in the haloalkane being selected from at least one of: F. cl, Br and I.
In still another preferred embodiment of the present invention, the iridium complex has a structural formula as shown in any one of formulas (40) to (51):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy. More preferably, the halogen is selected from at least one of the following: F. cl, Br and I. More preferably, the haloalkyl group is selected from at least one of: a single halo-substituted alkyl group, at least two same halo-substituted alkyl groups, at least two different halo-substituted alkyl groups, the halo in the haloalkane being selected from at least one of: F. cl, Br and I.
More preferably, the aromatic ring-linked nitrogen heterocyclic structure in the iridium complexThe following specific structure is possible:
more preferably, the nitrogen heterocyclic sulfonic acid structure in the iridium complexThe following specific structure is possible:
more preferably, the iridium complex may have a specific structure as follows:
the invention also discloses a preparation method of the iridium complex. The preparation method can prepare the iridium complex. Specifically, the preparation method comprises the following steps:
step S10: the iridium dimeric bridged complex, azacyclo-sulfonic acid and potassium carbonate are mixed, and then a 2-ethoxyethanol solution is added to obtain a first solution.
The iridium dimeric bridged complex is provided with an aromatic ring linked azacyclo serving as a first main ligand, and the second main ligand is azacyclo sulfonic acid.
Wherein the molar ratio of the iridium dimeric bridged complex to the azacyclo-sulfonic acid to the potassium carbonate is 1: 2-4: 5-10.
The aromatic ring-linked nitrogen heterocyclic ring serving as a first main ligand can be prepared by a method disclosed by a reference document to obtain (a) S.Lamansky, P.Djurovich, D.Murphy, F.Abdel-Razzaq, H.E.Lee, C.Adachi, P.E.Burrow, S.R.Forrest, M.E.Thompson, J.Am.chem.Soc., 2001, 123, 4304-containing material 4312; (b) S.Lamansky, P.Djurovich, D.Murphy, F.Abdel-Razzaq, R.Kwong, I.Tsyba, M.Bortz, B.Mui, R.Bau, M.E.Thompson, Inorg.chem., 2001, 40, 1704-.
Step S20: and heating the first solution for reaction, and cooling to obtain a second solution.
Wherein the heating reaction temperature is 120-140 ℃, and the reaction time is 12-24 h.
Step S30: the solvent of the second solution was removed and the organic phase was extracted.
The removal of the solvent can be achieved by distillation under reduced pressure. The extraction can be carried out with dichloromethane and water. The organic phase may be subjected to a concentration treatment.
Step S40: separating the organic phase by column chromatography to obtain the iridium complex with the structural formula shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
The iridium complex separated by column chromatography is a crude product. The purity of the iridium complex can reach the purity capable of being applied to an organic electroluminescent device by purifying the iridium complex through sublimation.
The iridium complex has the advantages of simple preparation method and high yield, and is flexible in chemical modification of aromatic ring linked nitrogen heterocycles serving as a first main ligand and nitrogen heterocyclic sulfonic acid serving as a second main ligand.
Based on the properties of the iridium complex, the invention also provides the application of the iridium complex in preparing organic electroluminescent devices.
The iridium complex can be applied to an organic electroluminescent device, and can obtain good device brightness and efficiency, thereby providing convenience for the design and production of an organic electroluminescent display and an illumination light source.
The invention also provides an organic electroluminescent device. The organic electroluminescent device includes: the organic electroluminescent device comprises a substrate, an anode, a hole transport layer, an organic electroluminescent layer, an electron transport layer and a cathode which are sequentially stacked. Wherein, the material of the organic electroluminescent layer comprises iridium complex. The structural formula of the iridium complex is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
The iridium complex is used as a phosphorescent material in the organic electroluminescent device, and is applied to an organic electroluminescent layer, so that the organic electroluminescent device has good device brightness and efficiency.
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The second primary ligand in example 1 is pyridine sulfonic acid
The first primary ligand of example 1 was prepared as follows: 2-bromopyridine (4.17g, 26.39mmol), 2, 4-difluorophenylboronic acid (5.00g, 31.66mmol), tetrakistriphenylphosphine palladium (0.91g, 0.79 mmol) and sodium carbonate (6.36g, 60.00mmol) were dissolved in 100mL tetrahydrofuran, refluxed for 24 hours, cooled, water and dichloromethane were added, and the organic layer was concentrated by column chromatography to give an aromatic ring diazacyclo ring as the first main ligand (3.84g, 76.18% yield).
Aromatic ring-linked nitrogen heterocycles (2.50g, 13.08mmol) and iridium trichloride (2.30g, 6.23mmol) as the first main ligand were dissolved in 15mL of ethoxyethanol, and the mixture was refluxed for 12h to give an iridium dimeric bridged complex.
Pyridine sulfonic acid (1.36g, 6.23mmol) and potassium carbonate (2.60g, 18.70mmol) were then added to the iridium dimeric bridged complex described above at 120. Refluxing at deg.C for 18 h. The system was cooled, water and methylene chloride were added, and the organic phase was concentrated and subjected to column chromatography to give iridium complex (1.01g, yield: 21.5%) as a yellow solid.
Specifically, the above process is as follows:
the structural formula of the iridium complex is as follows:
the nuclear magnetic resonance hydrogen spectrum of the iridium complex is as follows:1H NMR(400MHz，CDCl3，)：9.66(d，J＝5.5Hz，1H)，8.38(d，J＝8.8Hz，1H)，8.23(d，J＝8.4Hz，1H)，7.91(t，J＝5.8Hz，1H)，7.81-7.73(m，4H)，7.42-7.31(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)。EI，[M]calcd for C33H21F4IrN3O2P，731.05；found 731.02。
the ultraviolet-visible absorption spectrum and photoluminescence spectrum of the iridium complex of example 1 were measured at room temperature, and the results are shown in fig. 1.
Example 2
An organic electroluminescent device was prepared using the iridium complex of example 1 as a light-emitting material.
The classical structure of OLEDs devices is: the organic electroluminescent device comprises a substrate, an anode, a hole transport layer, an organic electroluminescent layer, an electron transport layer and a cathode which are sequentially stacked.
In example 2, the substrate was glass, the anode material was Indium Tin Oxide (ITO), and 4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline (TAPC) was used for the hole transport layer. The structural formula of the TAPC is as follows:the electron transport layer material uses 3, 3 ' - (5 ' - (3- (pyridine-3-yl) phenyl) - [1, 1 ': 3 ', 1 ' -triphenyl)]-3, 3 "-diyl) bipyridine (TmPyPB). The structural formula of TmPyPB is:the thickness is 60nm, and the evaporation rate is 0.05 nm/s. The cathode adopts LiF/Al, the thickness of LiF is 1nm, the evaporation rate is 0.01nm/s, the thickness of Al is 100nm, and the evaporation rate is 0.2 nm/s. The organic electroluminescent layer adopts a doped structure, and the main material is 1, 3-di (9H-carbazole-9-yl) benzene(mCP). The mCP has a structural formula as follows:the light-emitting material of the organic electroluminescent layer selected was the iridium complex prepared in example 1. The thickness is 40nm, the evaporation rate is 0.05nm/s, and the mass fraction of the iridium complex is 8%.
The prepared OLED device has the starting voltage of 2.9V, and the maximum power efficiency, the current efficiency and the external quantum efficiency are respectively 50.89lm/W, 50.99cd/A and 25.1 percent. The device reaches a maximum luminance of 34153cd/m at an applied voltage of 10.0V2The device is shown to be a blue light device with excellent performance. The result shows that the azacyclo-sulfonic acid is used as the second ring metal ligand to effectively synthesize the complex with high luminous performance and different colors, and the complex shows good device performance.
The performance of the OLED device of example 2 is shown in fig. 2 to 5. Fig. 2 is the electroluminescence spectrum of the OLED device of example 2. Fig. 3 is a graph of current efficiency as a function of current density for the OLED device of example 2. Fig. 4 is a graph of power efficiency as a function of current density for the OLED device of example 2. Fig. 5 is a graph of current density and luminance versus voltage for the OLED device of example 2.
The technical solutions of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the above examples are only used to help understand the core ideas of the present invention; meanwhile, for a person skilled in the art, according to the idea of the embodiment of the present invention, there may be a change in the specific implementation and application scope, and in summary, the content of the present specification should not be construed as a limitation to the embodiment of the present invention.
Claims (10)
1. An iridium complex is characterized in that the structural formula of the iridium complex is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstitutedAromatic ring, substituted or unsubstituted aromatic heterocycle of (A), Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
2. The iridium complex according to claim 1, wherein Ar is Ar2At least one selected from the group consisting of: substituted or unsubstituted benzene ring, substituted or unsubstituted pyridine ring.
3. The iridium complex according to claim 1, wherein Ar is Ar3At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted imidazolyl.
4. The iridium complex according to claim 1, wherein the iridium complex has a structural formula as shown in any one of the formulae (4) to (15):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy.
5. The iridium complex of claim 1, wherein: the structural formula of the iridium complex is shown as any one of formula (16) to formula (27):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy.
6. The iridium complex according to claim 1, wherein the iridium complex has a structural formula as shown in any one of the formulae (28) to (39):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy.
7. The iridium complex according to claim 1, wherein the iridium complex has a structural formula as shown in any one of formulae (40) to (51):
wherein R is1～R13Each selected from at least one of: H. halogen, alkyl, aryl, haloalkyl, methoxy.
8. A method for preparing an iridium complex, comprising:
mixing an iridium dimerization bridging complex, azacyclo-sulfonic acid and potassium carbonate, and then adding a 2-ethoxy ethanol solution to obtain a first solution, wherein the iridium dimerization bridging complex is provided with an aromatic ring linked azacyclo serving as a first main ligand, and the second main ligand is azacyclo-sulfonic acid;
heating the first solution for reaction, and cooling to obtain a second solution;
removing the solvent of the second solution, and extracting to obtain an organic phase;
and (2) separating the organic phase by column chromatography to obtain the iridium complex with the structural formula shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
9. Use of an iridium complex as claimed in any one of claims 1 to 7 in the preparation of an organic electroluminescent device.
10. An organic electroluminescent device comprising: the organic electroluminescent device comprises a substrate, an anode, a hole transport layer, an organic electroluminescent layer, an electron transport layer and a cathode which are sequentially stacked, and is characterized in that: the material of the organic electroluminescent layer comprises an iridium complex, and the structural formula of the iridium complex is shown as formula (1), formula (2) or formula (3):
wherein Ar is1At least one selected from the group consisting of: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted indazolyl, Ar2At least one selected from the group consisting of: substituted or unsubstituted aromatic ring, substituted or unsubstituted aromatic heterocycle, Ar3At least one selected from the group consisting of: substituted or unsubstituted nitrogen-containing heterocycles.
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| US20060163542A1 (en) * | 2004-09-10 | 2006-07-27 | Idemitsu Kosan Co., Ltd. | Metal-complex compound and organic electroluminescence device using the compound |
| JP2009094124A (en) * | 2007-10-04 | 2009-04-30 | Idemitsu Kosan Co Ltd | Organic electroluminescence device |
| CN103896990A (en) * | 2014-03-12 | 2014-07-02 | 石家庄诚志永华显示材料有限公司 | Organic electroluminescent material and application thereof |
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| CN1715363A (en) * | 2004-06-29 | 2006-01-04 | 三星Sdi株式会社 | Iridium (III) complex with heteroatom linking group and organic electroluminescent device using the complex |
| US20060163542A1 (en) * | 2004-09-10 | 2006-07-27 | Idemitsu Kosan Co., Ltd. | Metal-complex compound and organic electroluminescence device using the compound |
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| CN112759617A (en) * | 2021-01-06 | 2021-05-07 | 吉林奥来德光电材料股份有限公司 | Iridium-matched organic electroluminescent material and preparation method and application thereof |
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