CN112028944A - Organic iridium complex containing heteroatom, preparation method thereof and photoelectric device - Google Patents
Organic iridium complex containing heteroatom, preparation method thereof and photoelectric device Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 67
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- -1 nitro, hydroxyl Chemical group 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 5
- 125000004431 deuterium atom Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000005693 optoelectronics Effects 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 125000006746 (C1-C60) alkoxy group Chemical group 0.000 claims 1
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims 1
- 125000006745 (C2-C60) alkynyl group Chemical group 0.000 claims 1
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims 1
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 59
- 229910052757 nitrogen Inorganic materials 0.000 description 40
- 238000012360 testing method Methods 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 150000002503 iridium Chemical class 0.000 description 10
- 239000002346 layers by function Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MWTPXLULLUBAOP-UHFFFAOYSA-N 2-phenoxy-1,3-benzothiazole Chemical class N=1C2=CC=CC=C2SC=1OC1=CC=CC=C1 MWTPXLULLUBAOP-UHFFFAOYSA-N 0.000 description 1
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001090 Polyaminopropyl biguanide Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- PJVZQNVOUCOJGE-CALCHBBNSA-N chembl289853 Chemical compound N1([C@H]2CC[C@H](O2)N2[C]3C=CC=CC3=C3C2=C11)C2=CC=C[CH]C2=C1C1=C3C(=O)N(C)C1=O PJVZQNVOUCOJGE-CALCHBBNSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- LBFXFIPIIMAZPK-UHFFFAOYSA-N n-[4-[4-(n-phenanthren-9-ylanilino)phenyl]phenyl]-n-phenylphenanthren-9-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C2=CC=CC=C2C=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C3=CC=CC=C3C=2)C=C1 LBFXFIPIIMAZPK-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
- C09K2211/10—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic iridium complex containing heteroatoms, a preparation method thereof and a photoelectric device, belonging to the field of organic photoelectric materials, wherein the structural general formula of the organic iridium complex is as follows:
in the formula, R1、R2Represents at least one or no substituent, R3、R4、R5Represents a single or no substituent; r1、R2The substituent position is any position of the ring on which each is positioned; a is any one of C3-C10 naphthenic base and C3-C12 heterocyclic radical; b is any one of C3-C10 naphthenic base, C3-C12 heterocyclic radical and C6-C20 aryl; and the condition that the ring of A is isoquinoline and the ring of B is a benzene ring does not exist simultaneouslyThe method is described. According to the invention, the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic iridium complex can improve the current efficiency and the service life of the device after being used for an organic electroluminescent device.
Description
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an organic iridium complex containing heteroatoms, a preparation method thereof and a photoelectric device.
Background
Organic electroluminescence was discovered as early as the beginning of the 20 th century. The Pope et al, the university of New Yo rk, 1963, first reported electroluminescent devices of single-crystal anthracene, but the driving power industry was too high and the thickness was too thick to receive attention. Until 1987, Tang et al of kodak corporation in the united states, using Alq as a light emitting layer, has attracted great interest from scientists in various countries after a low voltage and high brightness device is obtained, and has become a research focus in the international world in the last decade, and the organic light emitting device has been developed rapidly.
The Organic Light Emitting Device (OLED) is composed of a cathode, an anode and organic layers inserted between the cathode and the anode, namely the device is composed of a transparent ITO anode, a hole injection layer (ETL), a Hole Transport Layer (HTL), a light Emitting Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and the cathode, and 1-2 organic layers can be omitted as required. The OLED has the action mechanism that voltage is formed between two electrodes, electrons are injected from a cathode on one side, holes are injected from an anode on the other side, the electrons and the holes are recombined in a light-emitting layer to form an excited state, the excited state returns to a stable ground state, and the device emits light.
And the light emitting material of the organic light emitting diode is mainly a phosphorescent light emitting material. The independent light emission of three primary colors of red, blue and green is the most adopted color mode at present, and the technical key point is to improve the color purity and efficiency of the luminescent material. Therefore, in recent years, research into organic phosphorescent materials has been conducted, and the most of them is a metal iridium complex.
As the light emitting material, excitons are formed by recombination of electrons and holes injected from each electrode. Singlet excitons emit fluorescence and triplet excitons emit phosphorescence. The singlet excitons emitted have a formation probability of 25%, while the triplet excitons emitting phosphorescence have a formation probability of 75%. Thus, triplet excitons provide greater current efficiency than singlet excitons. Among such phosphorescent materials, organic phosphorescent materials may have greater current efficiency than fluorescent materials. Therefore, organic phosphorescent materials are being widely studied as an important factor for improving the efficiency of organic electroluminescent devices.
However, the organic phosphor luminescent materials disclosed so far have certain disadvantages in current efficiency and life. Therefore, the development of a material with high current efficiency and long service life is a technical problem to be solved at present.
Disclosure of Invention
It is an object of embodiments of the present invention to provide a heteroatom-containing organic iridium complex to solve the problems set forth in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a heteroatom-containing organic iridium complex has a general structural formula of formula I:
in the formula, R1、R2Represents at least one or no substituent, R3、R4、R5Represents a single or no substituent; r1、R2The substituent position is any position of the ring on which each is positioned;
R1、R2、R3、R4、R5each independently is hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphoryl, substituted or unsubstituted alkyl of C1-C60, substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted cycloalkyl of C3-C60, substituted or unsubstituted alkoxy of C1-C60, substituted or unsubstituted alkylamino of C1-C60, substituted or unsubstituted C2 to C60 alkylene, substituted or unsubstituted C2 to C60 alkynyl, substituted or unsubstituted C2 to C60 heterocyclic group, substituted or unsubstituted C10 to C60 condensed ring group;
a is any one of C3-C10 naphthenic base and C3-C12 heterocyclic radical; b is any one of C3-C10 naphthenic base, C3-C12 heterocyclic radical and C6-C20 aryl; and the condition that the ring of A is isoquinoline and the ring of B is a benzene ring does not exist at the same time.
Preferably, R1、R2、R3、R4、R5Each independently is at least one of hydrogen, deuterium atom, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocyclic group, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted C10-C20 condensed ring group.
Preferably, in the formula, R3、R4、R5At least one of which is F.
Wherein the hydrogen atom in each of the above groups or substituents may be replaced by a deuterium atom.
Preferably, the organic iridium complex has the chemical formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, formula I-7, formula I-8, formula I-9, formula I-10, formula I-11, formula I-12, formula I-13, formula I-14, formula I-15, formula I-16, formula I-17, formula I-18, formula I-19, formula I-20, formula I-21, formula I-22, formula I-23, formula I-24, formula I-25, formula I-26, formula I-27, formula I-28, formula I-29, formula I-30, formula I-31, formula I-32, formula I-33, formula I-34, Formula I-35, formula I-36, formula I-37, formula I-38, formula I-39, formula I-40, formula I-41, formula I-42, formula I-43, formula I-44, formula I-45, formula I-46, formula I-47, formula I-48, formula I-49, formula I-50, formula I-51, formula I-52, formula I-53, formula I-54, formula I-55, formula I-56, formula I-57, formula I-58, formula I-59, formula I-60, formula I-61, formula I-62, formula I-63, formula I-64, formula I-65, formula I-66, formula I-67, formula I-68, formula I-69, formula I-70, formula I-71, Formula I-72, formula I-73, formula I-74, formula I-75, formula I-76, formula I-77, formula I-78, formula I-79, formula I-80, formula I-81, formula I-82, formula I-83, formula I-84, formula I-85, formula I-86, formula I-87, formula I-88, formula I-89, formula I-90, formula I-91, formula I-92, formula I-93, formula I-94, formula I-95, formula I-96, formula I-97, formula I-98, formula I-99, formula I-100, formula I-101, formula I-102, formula I-103, formula I-104, formula I-105, formula I-106, formula I-107, formula I-108, formula I-95, Formula I-109, formula I-110, formula I-111, formula I-112, formula I-113, formula I-114, formula I-115, formula I-116, formula I-117, formula I-118, formula I-119, formula I-120, formula I-121, formula I-122, formula I-123, formula I-124, formula I-125, formula I-126, formula I-127, formula I-128, formula I-129, formula I-130, formula I-131, formula I-132, formula I-133, formula I-134, formula I-135, formula I-136, formula I-137, formula I-138, formula I-139, formula I-140, formula I-141, formula I-142, formula I-143, formula I-144, formula I-145, Any one of formulae I-146, formulae I-147, formulae I-148, formulae I-149, formulae I-150, formulae I-151, formulae I-152, formulae I-153, formulae I-154, formulae I-155, formulae I-156, formulae I-157, formulae I-158, formulae I-159, formulae I-160:
another object of an embodiment of the present invention is to provide a preparation method of the above organic iridium complex, which includes the following steps:
taking a compound with a structural general formula of formula II and a compound with a structural general formula of formula III;
reacting a compound with a general formula II with iridium trichloride to obtain a compound with a general formula IV;
reacting a compound with a general formula IV and a compound with a general formula III to obtain the organic iridium complex;
preferably, in the step, the compound with the general structural formula II and the iridium trichloride are reacted in a mixed solution of ethylene glycol ethyl ether and water.
Further, the mol ratio of the compound with the structural general formula of formula II to the iridium trichloride is (2.2-2.8): 1; in the mixed solution of the ethylene glycol ethyl ether and water, the volume ratio of the ethylene glycol ethyl ether to the water is 3: 1; the dosage of the mixed solution is 15-30 times of that of iridium trichloride; the reaction time is preferably 24 to 30 hours.
Preferably, in the step, the compound with the general structural formula IV and the compound with the general structural formula III are reacted in ethylene glycol ether containing alkali.
Further, the molar ratio of the compound with the structural general formula IV to the compound with the structural general formula III is 1 (2.5-8); the dosage of the ethylene glycol ethyl ether is 10-30 times of that of the compound with the structural general formula IV; the reaction time is 10 to 30 hours, preferably 20 to 24 hours.
Preferably, the base is anhydrous potassium carbonate or anhydrous sodium carbonate.
Another object of the embodiments of the present invention is to provide an application of the above organic iridium complex in the preparation of organic electroluminescent devices.
It is another object of an embodiment of the present invention to provide an optoelectronic device, including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer including the above-mentioned organic iridium complex.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the organic iridium complex.
Preferably, the mass ratio of the host material to the doping material is (90-99.5): (0.5-10).
Specifically, the first electrode is an anode, the type of which is not particularly limited, and may be a conventional anode known to those skilled in the art, and more preferably is one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide, and the thickness of the first electrode is 10 to 500 nm. The second electrode is a cathode, the kind of which is not particularly limited, and is a conventional cathode known to those skilled in the art, and more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb, and the thickness of the second electrode is 100 to 1000 nm.
The main material is preferably one or more of 4, 4'-N, N' -biphenyl dicarbazole (CBP), octahydroxyquinoline (Al q3), metal phenoxybenzothiazole compounds, polyfluorene, aromatic condensed rings and zinc complexes. The thickness of the light emitting layer is 10 to 500 nm.
In addition, the organic layer may further include other functional layers, and the other functional layers may be specifically selected from one or more of the following functional layers: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a hole injection-hole transport functional layer (i.e., having both hole injection and hole transport functions), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and an electron transport-electron injection functional layer (i.e., having both electron transport and electron injection functions).
The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art.
Preferably: the hole injection layer is one of 2-TNATA (namely N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine), phthalocyanine and porphyrin compounds, starburst triarylamine, a conductive polymer, an N-type semiconductive organic complex and a metal organic complex, and the thickness of the hole injection layer is 10-500 nm.
The hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1, 1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine) arylamine carbazole compound and indolocarbazole compound, and the thickness of the hole transport layer is 10-500 nm.
The hole blocking layer is one of BAlq, BCP and BPhen, and the thickness of the hole blocking layer is 10-500 nm.
The electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives, and the thickness of the electron transport layer is 10-500 nm.
The electron injection layer is LiF, CsF or Li2O、Al2O3And MgO with a thickness of 0.1-10 nm.
In the embodiment of the present invention, the above light emitting layer and other various functional layers may be formed by a solution coating method and a vacuum deposition method. The solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, etc., but is not limited thereto.
The above-mentioned photoelectric device may be an organic electroluminescent device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or the like, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the organic iridium complex containing the heteroatom, the specific heterocyclic ligand combination is selected, the wavelength of the compound is adjusted, and the obtained organic iridium complex can remarkably improve the current efficiency of a photoelectric device and prolong the service life of the photoelectric device after being used for the photoelectric device such as an organic electroluminescent device. In addition, the preparation method of the organic iridium complex provided by the embodiment of the invention has the advantages of simple process and high purity of the prepared product, and can be applied to industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Complex example 1
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as a formula I-4 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) ligand II-4 (13.27g, 50mmol), IrC1, was weighed out under nitrogen protection3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 330mL of ethylene glycol ethyl ether and 110mL of purified water is added, the mixture is refluxed for 25 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain dark red powderThe bridged ligand IV-4, having a mass of 8.17g, was present in a yield of 54%.
(2) Then weighing the bridging ligand IV-4 (7.56g, 5mmol), adding anhydrous potassium carbonate (6.9g, 50mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-4 (1.89g, 15mmol) under nitrogen, refluxing for 24 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic iridium complex shown in the formula I-4, wherein the mass of the organic iridium complex is 3.72g, the yield is 44%, and the HPLC purity is more than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 846.03; the test value was 846.27.
The calculated value of the elemental analysis (%) > is C: 58.21; h is 5.24; f is 6.74; 22.72 parts of Ir; n is 3.31; o is 3.78; test value C is 58.23; h is 5.25; f is 6.75; 22.70 parts of Ir; n is 3.31; o is 3.76.
As can be seen by comparing the calculated values with the test values, the measured values are substantially consistent with the theoretical values, thereby proving that the organic iridium complex with the structural formula I-4 can be successfully synthesized by the complex example.
Complex example 2
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as the formula I-36 in the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) ligand II-36 (14.60g, 46mmol), IrC1 was weighed out under nitrogen protection3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 360mL of ethylene glycol ethyl ether and 120mL of purified water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered, water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence, and bridge-linking powder of dark red powder is obtainedLigand IV-36, weight 10.96g, yield 64%.
(2) Then weighing the bridging ligand IV-36 (10.27g, 6mmol), adding anhydrous potassium carbonate (9.11g, 66mmol), adding 180ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-36 (4.97g, 20mmol) under nitrogen, refluxing for 22 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Dichloromethane and toluene are used as solvents, neutral alumina column chromatography is carried out, filtrate is concentrated and solid is separated out, and finally the organic iridium complex shown in the formula I-36 is obtained, the mass is 5.41g, the yield is 42%, and the HPLC purity is more than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 1072.46; the test value was 1072.46.
The calculated value of the elemental analysis (%) > is C: 66.08; h is 6.86; f is 3.54; 17.92 parts of Ir; 2.61 of N; o is 2.98; test value C: 66.07; h is 6.84; f is 3.53; 17.94 parts of Ir; 2.63 of N; o is 2.98.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agree with the theoretical values, thereby proving that the organic iridium complexes of the structural formulae I to 36 can be successfully synthesized by the above complex examples.
Complex example 3
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as a formula I-61 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) ligand II-61 (13.89g, 48mmol), IrC1 was weighed out under nitrogen protection3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 360mL of ethylene glycol ethyl ether and 120mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain dark redThe bridging ligand IV-61 of the powder, having a mass of 9.81g, was found to be 61% yield.
(2) Then weighing the bridging ligand IV-61 (9.65g, 6mmol), adding anhydrous potassium carbonate (9.11g, 66mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-61 (6.74g, 18mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic iridium complex shown in the formula I-61, wherein the mass of the organic iridium complex is 5.89 g. The yield was 43% and the HPLC purity was greater than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 1142.28; the test value was 1142.49.
The calculated value of the elemental analysis (%) > is C: 57.83; h is 5.12; f is 14.97; 16.83 parts of Ir; 2.45 of N; o is 2.80; test value C: 57.82; h is 5.10; f, 14.96; 16.83 parts of Ir; 2.47 of N; o is 2.82.
As can be seen by comparing the calculated values with the test values, the measured values are substantially consistent with the theoretical values, thereby proving that the organic iridium complexes with the structural formula I-61 can be successfully synthesized by the complex examples.
Complex example 4
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as the formula I-84 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) ligand II-84 (12.73g, 44mmol), IrC1 were weighed out under nitrogen protection3·3H2O (7.05g, 20mmo1) is put into a reaction system, mixed solution of 420mL of ethylene glycol ethyl ether and 140mL of purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain darkThe red powder of bridged ligand IV-84 was 10.30g in mass, 64% yield.
(2) Then weighing the bridging ligand IV-84 (9.65g, 6mmol), adding anhydrous potassium carbonate (9.11g, 66mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-84 (3.78g, 18mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic iridium complex shown in the formula I-84, wherein the mass of the organic iridium complex is 6.10g, the yield is 52%, and the HPLC purity is more than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 978.23; the test value was 978.56.
The calculated value of the elemental analysis (%) > is C: 62.62; h is 5.77; f is 5.83; 19.65 parts of Ir; 2.86 of N; o is 3.27; the test value is C: 62.60; h is 5.79; f is 5.84; 19.67 parts of Ir; 2.85 of N; o is 3.25.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agree with the theoretical values, thereby proving that the organic iridium complexes of the formulae I to 84 can be successfully synthesized by the above complex examples.
Complex example 5
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as the formula I-95 in the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) ligand II-95 (19.11g, 56mmol), IrC1, was weighed out under nitrogen protection3·3H2O (7.05g, 20mmo1) is put into a reaction system, mixed solution of 450mL of ethylene glycol ethyl ether and 150mL of purified water is added, reflux is carried out for 28 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence to obtain the productThe bridging ligand IV-95 was a dark red powder with a mass of 12.17g and a yield of 67%.
(2) Then weighing the bridging ligand IV-95 (11.81g, 6.5mmol), adding anhydrous potassium carbonate (8.97g, 65mmol), adding 200ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-95 (9.24g, 32.5mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic iridium complex shown in the formula I-95, wherein the mass of the organic iridium complex is 5.11g, the yield is 34%, and the HPLC purity is more than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 1156.13; the test value was 1156.72.
Elemental analysis (%): calculated value is C57.14; h is 3.05; f is 13.15; 16.63 parts of Ir; n is 7.27; o is 2.77; test value C: 57.13; h is 3.04; f is 13.13; ir of 16.64; n is 7.28; o is 2.79.
As can be seen by comparing the calculated values with the test values, the measured values are substantially consistent with the theoretical values, thereby proving that the organic iridium complexes with the structural formula I-95 can be successfully synthesized by the complex examples.
Complex example 6
The embodiment of the complex provides an organic iridium complex containing hetero atoms, the chemical structural formula of the complex is shown as formula I-153 in the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing the formula II-153 (14.36g, 48mmol), IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 360mL of ethylene glycol ethyl ether and 120mL of purified water is added, the mixture is refluxed for 28 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for flushing in sequenceWashing and drying to obtain the bridging ligand IV-153 of dark red powder, wherein the mass is 7.91g, and the yield is 48%.
(2) Then weighing the bridging ligand IV-153 (7.42g, 4.5mmol), adding anhydrous potassium carbonate (6.21g, 45mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-153 (5.09g, 22.5mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic iridium complex shown in the formula I-153, wherein the mass of the organic iridium complex is 2.65g, the yield is 29%, and the HPLC purity is more than 99.5%.
In addition, the mass spectrum of the organic iridium complex is calculated as 1013.49; the test value was 1013.72.
Elemental analysis (%): calculated value is C: 32.00; 43.11 is used as a reference material; 18.97 of Ir; n is 2.76; o is 3.16, and the test value is C is 32.01; f is 43.13; 18.98 parts of Ir; n is 2.74; o is 3.14.
As can be seen by comparing the calculated values with the test values, the measured values are substantially consistent with the theoretical values, thereby proving that the organic iridium complexes with the structural formula I-153 can be successfully synthesized by the complex examples.
Examples 7 to 16 of the complexes
Because the synthetic route and the principle of the preparation method of other organic iridium complexes with the structural general formula of formula I in the invention content are the same as those of the listed complex example 1, the corresponding organic iridium complexes can be obtained only by respectively replacing ligands with compounds corresponding to the corresponding ligand structures in the target product and correspondingly adjusting the material dosage according to the corresponding stoichiometric ratio, so that the method is not exhaustive, and a plurality of organic iridium complexes are selected as the complex examples 7-21 in the invention, and are specifically shown in the following table 1.
TABLE 1
The embodiment of the invention also provides a photoelectric device prepared by using the organic iridium complex provided by the embodiment, and particularly, the photoelectric device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.
The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer and a composite layer of electron injection technical layers, and at least one layer may or may not include the organic iridium complex.
Specifically, the light-emitting layer includes a host material and a dopant material; wherein, the host material can be 4, 4'-N, N' -biphenyl dicarbazole (CBP), but is not limited thereto; the doping material can be selected from the organic iridium complexes.
In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.
Device example 1
The device embodiment 1 provides an organic electroluminescent device, and a manufacturing method thereof includes the steps of:
(1) coating with a thickness of
The ITO glass substrate of (1) was cleaned in distilled water for 2 times, ultrasonically cleaned for 30 minutes, repeatedly cleaned with distilled water for 2 times, ultrasonically cleaned for 10 minutes, and after the cleaning with distilled water was completed, the substrate was dried after sequentially ultrasonically cleaned with solvents of isopropyl alcohol, acetone, and methanol (each time, 10 minutes), transferred to a plasma cleaning machine, cleaned for 5 minutes, and sent to an evaporation coater.
(2) Under vacuum conditions, the standard pressure was set at 1X 10-6The support, which takes ITO as the anode,first vapor-depositing thereon
Then sequentially evaporating
A mixture of the host substance 4, 4'-N, N' -Biphenyldicarbazole (CBP) and the above-mentioned organic iridium complex I-1 ((II))
Wherein the weight ratio of the 4, 4'-N, N' -biphenyl dicarbazole to the organic iridium complex I-1 is 95:5), and an electron transport layer
Electron injection layer
Cathode electrode
And the organic electroluminescent device can be prepared.
Wherein, CuPc, NPB, CBP, Alq3The structural formula of (A) is as follows:
device examples 2 to 21
An organic electroluminescent device was fabricated by referring to the fabrication method provided in device example 1 above, except that the organic iridium complex i-1 (dopant) in device example 1 above was replaced with the organic iridium complexes of formulae i-4, i-14, i-23, i-30, i-36, i-42, i-54, i-61, i-70, i-80, i-84, i-95, i-100, i-111, i-120, i-127, i-129, i-140, i-148, and i-153 above, respectively, to fabricate a corresponding organic electroluminescent device.
Comparative device example 1
Preparation method provided with reference to device example 1 aboveAn organic electroluminescent device was prepared, except that the organic iridium complex I-1 (dopant) in the above device example 1 was replaced with the existing iridium metal complex (btp)2Ir (acac), where (btp)2The structural formula of Ir (acac) is as follows:
experimental example:
the performance and the light emitting characteristics of the organic electroluminescent devices obtained in the device examples 1 to 21 and the device comparative example 1 were respectively tested under the same current conditions by using a KEITHLEY model 2400 source measuring unit and a CS-2000 spectroradiometer to evaluate the driving voltage, the current efficiency and the light emitting life of the organic electroluminescent device (T95), and the specific test results are shown in table 2.
TABLE 2
From Table 2 above, it can be seen that the ratio (btp) is higher than that provided in comparative device example 12The organic electroluminescent device prepared by using the organic iridium complex provided by the embodiment of the invention as the doping material can effectively reduce the driving voltage of a photoelectric device, and can remarkably improve the current efficiency and service life of the organic electroluminescent device.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An organic iridium complex containing heteroatoms, which is characterized in that the structural general formula of the organic iridium complex is as shown in formula I:
in the formula, R1、R2Represents at least one or no substituent, R3、R4、R5Represents a single or no substituent; r1、R2The substituent position is any position of the ring on which each is positioned;
R1、R2、R3、R4、R5each independently is at least one of hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkylene, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C2-C60 heterocyclic group and substituted or unsubstituted C10-C60 condensed ring group;
a is any one of C3-C10 naphthenic base and C3-C12 heterocyclic radical; b is any one of C3-C10 naphthenic base, C3-C12 heterocyclic radical and C6-C20 aryl; and the condition that the ring of A is isoquinoline and the ring of B is a benzene ring does not exist at the same time.
2. The heteroatom-containing organic iridium complex of claim 1 wherein R1、R2、R3、R4、R5Each independently is hydrogen, deuterium atom, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocyclic, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C,At least one of substituted or unsubstituted C10-C20 condensed ring group.
3. The organic iridium complex containing hetero atoms according to claim 1, wherein R is3、R4、R5At least one of which is F.
4. The heteroatom-containing organic iridium complex of claim 1, wherein the chemical formula of the organic iridium complex is represented by formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, formula I-7, formula I-8, formula I-9, formula I-10, formula I-11, formula I-12, formula I-13, formula I-14, formula I-15, formula I-16, formula I-17, formula I-18, formula I-19, formula I-20, formula I-21, formula I-22, formula I-23, formula I-24, formula I-25, formula I-26, formula I-27, formula I-28, formula I-29, formula I-30, Formula I-31, formula I-32, formula I-33, formula I-34, formula I-35, formula I-36, formula I-37, formula I-38, formula I-39, formula I-40, formula I-41, formula I-42, formula I-43, formula I-44, formula I-45, formula I-46, formula I-47, formula I-48, formula I-49, formula I-50, formula I-51, formula I-52, formula I-53, formula I-54, formula I-55, formula I-56, formula I-57, formula I-58, formula I-59, formula I-60, formula I-61, formula I-62, formula I-63, formula I-64, formula I-65, formula I-66, formula I-67, Formula I-68, formula I-69, formula I-70, formula I-71, formula I-72, formula I-73, formula I-74, formula I-75, formula I-76, formula I-77, formula I-78, formula I-79, formula I-80, formula I-81, formula I-82, formula I-83, formula I-84, formula I-85, formula I-86, formula I-87, formula I-88, formula I-89, formula I-90, formula I-91, formula I-92, formula I-93, formula I-94, formula I-95, formula I-96, formula I-97, formula I-98, formula I-99, formula I-100, formula I-101, formula I-102, formula I-103, formula I-104, Formula I-105, formula I-106, formula I-107, formula I-108, formula I-109, formula I-110, formula I-111, formula I-112, formula I-113, formula I-114, formula I-115, formula I-116, formula I-117, formula I-118, formula I-119, formula I-120, formula I-121, formula I-122, formula I-123, formula I-124, formula I-125, formula I-126, formula I-127, formula I-128, formula I-129, formula I-130, formula I-131, formula I-132, formula I-133, formula I-134, formula I-135, formula I-136, formula I-137, formula I-138, formula I-139, formula I-140, formula I-141, Any one of formulae I-142, formulae I-143, formulae I-144, formulae I-145, formulae I-146, formulae I-147, formulae I-148, formulae I-149, formulae I-150, formulae I-151, formulae I-152, formulae I-153, formulae I-154, formulae I-155, formulae I-156, formulae I-157, formulae I-158, formulae I-159, formulae I-160:
5. a method for preparing an organic iridium complex according to any one of claims 1 to 4, comprising the steps of:
taking a compound with a structural general formula of formula II and a compound with a structural general formula of formula III;
reacting a compound with a general formula II with iridium trichloride to obtain a compound with a general formula IV;
reacting a compound with a general formula IV and a compound with a general formula III to obtain the organic iridium complex;
6. the method for preparing an organic iridium complex according to claim 5, wherein in the step, the compound having the general structural formula II and iridium trichloride are reacted in a mixed solution of ethylene glycol ethyl ether and water.
7. The method according to claim 5, wherein the compound of formula IV is reacted with the compound of formula III in the presence of a base in ethylene glycol ether.
8. The method according to claim 7, wherein the base is anhydrous potassium carbonate.
9. An optoelectronic device comprising a first electrode, a second electrode and at least one organic layer disposed between said first electrode and said second electrode, wherein said organic layer comprises an organic iridium complex according to any one of claims 1 to 4.
10. The optoelectronic device according to claim 9, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the organic iridium complex.
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