CN108484677A - A kind of pyridine structure contained feux rouges metal complex - Google Patents
A kind of pyridine structure contained feux rouges metal complex Download PDFInfo
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- CN108484677A CN108484677A CN201810089714.2A CN201810089714A CN108484677A CN 108484677 A CN108484677 A CN 108484677A CN 201810089714 A CN201810089714 A CN 201810089714A CN 108484677 A CN108484677 A CN 108484677A
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 27
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 13
- 229910052805 deuterium Inorganic materials 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 claims description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 24
- 150000001875 compounds Chemical group 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 cycloalkyl radicals Chemical class 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 125000006413 ring segment Chemical group 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YWWZASFPWWPUBN-UHFFFAOYSA-N 1-bromoisoquinoline Chemical compound C1=CC=C2C(Br)=NC=CC2=C1 YWWZASFPWWPUBN-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical group C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001768 cations Chemical class 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
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 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
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CLTPAQDLCMKBIS-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-1-ylamino)phenyl]phenyl]-n-naphthalen-1-ylnaphthalen-1-amine Chemical compound C1=CC=C2C(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 CLTPAQDLCMKBIS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
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)
- Pyridine Compounds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to field of organic electroluminescent materials, disclose a kind of pyridine structure contained feux rouges metal complex.The there is provided metal complex of invention has the general formula structure as shown in formula (I).The present invention significantly improves purifying and the distillation yield of material by introducing specific assistant ligand into compound structure, extremely advantageous to industrialized production to reduce the use cost of material.The metal complex of the application can make material have similar photoelectric properties, can more mitigate luminescence queenching situation, improve the quantum efficiency of organic electroluminescence device, greatly improve luminous efficiency.
Description
Technical Field
The invention belongs to the field of organic electroluminescent materials, and particularly relates to a pyridine-structured red light metal complex and application thereof.
Background
In recent years, a great deal of research shows that iridium complexes are considered to be the most ideal choice for OLEDs (organic electroluminescent devices) as well as numerous heavy metal element complexes, iridium atoms with 5d76s2 outer-layer electronic structure have 5d6 electronic configuration after forming + 3-valent cations, have stable hexa-coordinated octahedral structure, so that the material has high chemical stability and thermal stability, and meanwhile, Ir (III) has a large spin-orbit coupling constant (ξ ═ 3909cm < -1 >), which is beneficial for improving the internal quantum yield of the complexes and reducing the luminescent life, thereby improving the overall performance of the luminescent device.
As a phosphorescent material, the iridium complex generally has a microsecond order, and easily causes phosphorescence quenching between a triplet-triplet state and a triplet-exciton of the iridium complex. In addition, in the current commonly used materials, the hole mobility of the hole transport material is much higher than the electron mobility of the electron transport material, and the commonly used host material is mainly used for hole transport, which results in the accumulation of a large amount of excess holes at the interface of the light emitting layer and the electron transport layer. Both of these factors result in reduced efficiency and severe efficiency roll-off. Researches show that if the iridium complex has higher electron transmission capability, the iridium complex can effectively increase the transmission and distribution of electrons in a light-emitting layer, widen an electron-hole region and balance the number of electron-hole pairs, greatly improve the efficiency of a device and reduce the roll-off of the efficiency.
CN106432346A discloses an iridium complex, a preparation method thereof and an electroluminescent device using the iridium complex, which comprises two main ligands and an auxiliary ligand, wherein the main ligands are 2- (4, 6-ditrifluoromethylpyridine-3-) quinoline, 2- (4, 6-ditrifluoromethylpyridine-4-) quinoline, 2- (4, 6-ditrifluoromethylpyridine-3-) isoquinoline, 2- (4, 6-ditrifluoromethylpyridine-4-) isoquinoline, 2- (4, 6-ditrifluoromethylpyridine-3-) quinazoline, 2- (4, 6-ditrifluoromethylpyridine-4-) quinazoline, 2- (4, 6-ditrifluoromethylpyridine-3-) phthalazine, Any one of 2- (4, 6-bis (trifluoromethyl) pyridine-4-) phthalazine derivatives, wherein the auxiliary ligand is acetylacetone or dibenzoyl methane. That is, the patent protects only two metal complexes of ancillary ligand structures.
Disclosure of Invention
The invention aims to provide a red-light metal complex with a pyridine structure, which can reduce the light quenching condition, improve the luminous efficiency, improve the purification and sublimation yield of materials and reduce the use cost of the materials.
Another object of the present invention is to provide a use of the above red-emitting metal complex in luminescent materials.
The object of the invention can be achieved by the following measures:
a metal complex with a structure shown as a formula (I),
wherein,
R1、R2or R3Each independently represents a fluorine atom, C1-6Alkyl radical, C1-6Fluoroalkyl or cyano, and R1、R2And R3At least one of them being a fluorine atom or C1-6A fluoroalkyl group;
o, p or q are each independently 0, 1 or 2, and the sum of o, p and q is not more than 3;
a is a nitrogen-containing heterocycle;
b is substituted or unsubstituted aromatic ring or heterocycle, and the substituent is selected from halogen and C1-6Alkyl or C1-6One or more of haloalkyl;
x is 1, 2 or 3;
m is a metal atom of group VIII, group IB, group IA or group IIA;
m is 2 or 3;
l is a group of formula (II):
G1、G2or G3Each independently is hydrogen, deuterium, substituted or unsubstituted C1-8Alkyl or substituted or unsubstituted C3-12Aryl with substituents selected from deuterium, halogen, C1-6Alkyl radical, C1-6Haloalkyl or C3-6One or more cycloalkyl radicals, and when G2When it is hydrogen, G1And G3Is not methyl or phenyl;
n is 1 or 0.
In a preferred embodiment, R1、R2Or R3Each independently represents hydrogen or C1-6A fluoroalkyl group.
In a more preferred embodiment, R1Or R2Each independently represents C1-4Fluoroalkyl radical, R3Represents hydrogen.
In another more preferred embodiment, R1Or R2Each independently represents trifluoromethyl or fluoroethyl, R3Represents hydrogen.
In a preferred embodiment, a is a pyridine ring.
In a preferred embodiment, B is a substituted or unsubstituted benzene or pyridine ring, and x is 1.
In a more preferred embodiment, A and B together form a group having the structure:
in a preferred embodiment, M is an Ir, Pt, Os, Ru or Au atom, more preferably, M is an Ir atom and M is 2.
In a preferred embodiment, G in the group of formula (II)1Is substituted or unsubstituted C1-8Alkyl, phenyl, furyl or thienyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group.
In a more preferred embodiment, G in formula (II)1Is trifluoromethyl, substituted or unsubstituted C2-8Alkyl, phenyl, furyl or thienyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group.
In a preferred embodiment, G in the group of formula (II)2Is hydrogen, deuterium, C1-4Alkyl radical, C1-4Haloalkyl or C1-4A deuterated alkyl group.
In a preferred embodiment, G in the formula (II)3Is substituted or unsubstituted C1-8Alkyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group.
In a more preferred embodiment, G in formula (II)3Is trifluoromethyl, substituted or unsubstituted C2-8Alkyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group.
In a preferred embodiment, n is 1.
In a preferred embodiment, L is selected from one of the following groups L5-1-43:
in a preferred embodiment, the metal complex of formula (I) in the present invention may be selected from:
unless otherwise indicated, the following terms used in the specification and claims have the meanings discussed below:
"alkyl" means a saturated aliphatic radical of 1 to 20 carbon atoms, including straight and branched chain radicals (a numerical range referred to herein, e.g., "1 to 20", means that the radical, in this case alkyl, may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). Preferably, the alkyl group is a medium size alkyl group having 1 to 10 carbon atoms, and more preferably, the alkyl group is an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl, etc.
"haloalkyl" means an alkyl group having one or more halo substituents, such as-CH2Cl、-CF3、-CH2CF3、-CH2CCl3And the like.
"fluoroalkyl" means an alkyl group having one or more fluorine substituents, such as-CH2F、-CF3、-CH2CF3、-CH2CF3And the like.
"Nitrogen-containing heterocycle" means a monocyclic or fused ring group of 5 to 12 ring atoms containing one, two, three or four N ring heteroatoms, the remaining ring atoms being C or other heteroatoms, and which may or may not have a completely conjugated pi-electron system. Non-limiting examples are pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrimidine, pyridine, quinoline, isoquinoline, purine, triazine, carbazole, pyrrolidinyl, piperidino, piperazino, morpholino, and the like.
An "aromatic ring" means an all-carbon monocyclic or fused polycyclic group of 6 to 12 carbon atoms having a completely conjugated pi-electron system. Non-limiting examples of aryl groups are phenyl, naphthyl and anthracenyl.
"heterocycle" means a monocyclic or fused ring group of 5 to 12 ring atoms containing one, two, three or four ring heteroatoms selected from N, O or S, the remaining ring atoms being C, and additionally having or not having a completely conjugated pi-electron system.
"cycloalkyl" means a monocyclic or fused ring all carbon (by "fused" ring is meant that each ring in the system shares an adjacent pair of carbon atoms with other rings in the system) group in which one or more rings do not have a fully attached pi-electron system, examples of cycloalkyl (without limitation) being cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, adamantane, cyclohexadiene, cycloheptane, and cycloheptatriene.
"cyano" means a-CN group.
"deuterium" means an isotope D of hydrogen.
"halogen" means fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
The metal complex can be applied to luminescent materials, in particular to luminescent materials of electroluminescent devices.
The inventors have found that the introduction of specific auxiliary ligands, in particular auxiliary ligands with longer carbon chains as in the present application, is significant for the improvement of the purification and sublimation yields of the material, thereby reducing the use cost of the material and being extremely advantageous for industrial production.
In addition, the auxiliary ligand and other corresponding groups adopted in the structure of the formula (I) of the metal complex can enable the material to have similar photoelectric properties, unexpectedly reduce the luminescence quenching condition, improve the quantum efficiency of the organic electroluminescent device and greatly improve the luminescence efficiency compared with other existing materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the following examples. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present invention in its various embodiments. However, the technical solutions claimed in the claims of the present invention can be implemented without these technical details and with various changes and modifications based on the following embodiments. Comparative example 1: synthesis of comparative Compound CC-1
1-bromoisoquinoline (26.39mmol), 2, 6-bis (trifluoromethyl) pyridine-3-boric acid (31.66mmol), tetrakistriphenylphosphine palladium (0.79mmol) and sodium carbonate (60.00mmol) were dissolved in 100mL tetrahydrofuran, reacted at 65 ℃ for 24 hours, cooled, added with water and dichloromethane, and the organic layer was concentrated by column chromatography to give the main ligand (CC-1-L). The main ligand (13.08mmol) and iridium trichloride (6.23mmol) were dissolved in 15mL of 2-ethoxyethanol, the mixture was reacted at 130 ℃ for 12h, cooled, added with water, and filtered to give the chloro-bridged intermediate (CC-1-Cl). The obtained chloro-bridged intermediate was added to 15mL of 2-ethoxyethanol without column chromatography, followed by the addition of the ancillary ligands acetylacetone (12.46mmol) and sodium carbonate (31.15mmol), and reacted at 130 ℃ for 12 hours. The system is cooled, water and dichloromethane are added, the organic layer is concentrated and subjected to column chromatography to obtain the compound CC-1, and the yield is 45%.
Examples 1 to 4: synthesis of Ir-1 to Ir-4
The synthesis was performed in the same manner as in comparative example CC-1, except that the acetylacetone ligand was replaced with the corresponding other ligand. Wherein Ir-1 adopts Ir-A1 ligand, Ir-2 adopts Ir-A2 ligand, Ir-3 adopts Ir-A3 ligand and Ir-4 adopts Ir-A4 ligand.
Examples 5 to 8: synthesis of Ir-5 to Ir-8
The synthesis was carried out in the same manner as in comparative example CC-1, except that the acetylacetone ligand was replaced with the corresponding other ligand, and 1-bromoisoquinoline was replaced with 2-bromoquinoline. Wherein Ir-5 adopts Ir-A1 ligand, Ir-6 adopts Ir-A2 ligand, Ir-7 adopts Ir-A3 ligand and Ir-8 adopts Ir-A4 ligand.
The relevant synthesis yields and mass spectral data are as follows. Mass spectral data were measured using an MTQ III q-TOF apparatus using an electrospray ion source.
| Compound (I) | Synthetic yield | Mass spectral data |
| Ir-1 | 55％ | 1069.4 |
| Ir-2 | 60％ | 1083.5 |
| Ir-3 | 68％ | 1125.5 |
| Ir-4 | 53％ | 1139.5 |
| Ir-5 | 63％ | 1071.3 |
| Ir-6 | 64％ | 1085.6 |
| Ir-7 | 69％ | 1127.5 |
| Ir-8 | 58％ | 1141.6 |
Device embodiments
In order to schematically illustrate the excellent characteristics of the material of the present invention, there is also provided an organic electroluminescent device, the structure of the OLED device comprising: the organic light emitting diode comprises a substrate, an anode, a hole transport layer, an organic light emitting layer, an electron transport layer and a cathode.
In the device manufacturing process, the substrate is glass, and the anode material is indium tin oxide; the hole transport layer uses N, N, N ', N' -tetra (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, the electron transport layer uses 3,3'- (5' - (3- (pyridine-3-yl) phenyl) - [1,1':3',1 '-triphenyl ] -3, 3' -diyl) bipyridine, the thickness is 60nm, the evaporation rate is 0.05 nm/s; LiF/Al is adopted as the cathode. The organic light-emitting layer adopts a light-emitting layer with a doped structure, and comprises a main material and a light-emitting material, wherein the main material is 2,2 '-bis (trifluoromethyl) -4,4' -bis (9-carbazole) biphenyl, and the selected light-emitting material is the iridium complex, and the mass fraction of the iridium complex is 5 wt%.
The external quantum efficiency of the device using compound CC-1 is defined as 100. The relevant data are detailed in table 1.
TABLE 1
| Luminescent material of device | Sublimation yield | Quantum efficiency |
| Ir-1 | 50.7％ | 106 |
| Ir-2 | 50.8％ | 107 |
| Ir-3 | 52.3％ | 108 |
| Ir-4 | 52.8％ | 107 |
| Ir-5 | 54.4％ | 114 |
| Ir-6 | 53.7％ | 114 |
| Ir-7 | 54.3％ | 113 |
| Ir-8 | 53.2％ | 112 |
| CC-1 | 35.2％ | 100 |
It can be seen that the compounds of the present invention have significantly improved quantum efficiency, synthesis yield and sublimation yield, especially sublimation yield, relative to the comparative compounds.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (10)
1. A metal complex with a structure shown as a formula (I),
wherein,
R1、R2or R3Each independently represents a fluorine atom, C1-6Alkyl radical, C1-6Fluoroalkyl or cyano, and R1、R2And R3At least one of them being a fluorine atom or C1-6A fluoroalkyl group;
o, p or q are each independently 0, 1 or 2, and the sum of o, p and q is not more than 3;
a is a nitrogen-containing heterocycle;
b is substituted or unsubstituted aromatic ring or heterocycle, and the substituent is selected from halogen and C1-6Alkyl or C1-6One or more of haloalkyl;
x is 1, 2 or 3;
m is a metal atom of group VIII, group IB, group IA or group IIA;
m is 2 or 3;
l is a group of formula (II):
G1、G2or G3Each independently is hydrogen, deuterium, substituted or unsubstituted C1-8Alkyl or substituted or unsubstituted C3-12Aryl with substituents selected from deuterium, halogen, C1-6Alkyl radical, C1-6Haloalkyl or C3-6One or more cycloalkyl radicals, and when G2When it is hydrogen, G1And G3Not methyl or phenyl at the same time;
n is 1 or 0.
2. The metal complex of formula (I) according to claim 1, wherein R1、R2Or R3Each independently represents hydrogen or C1-6A fluoroalkyl group.
3. The metal complex represented by the formula (I) according to claim 1, wherein a is a pyridine ring.
4. The metal complex represented by the formula (I) according to claim 1, wherein B is a substituted or unsubstituted benzene ring or pyridine ring, and x is 1.
5. The metal complex of formula (I) according to claim 4, wherein a and B together form a group having the structure:
6. the metal complex represented by the formula (I) according to claim 1, wherein M is an Ir atom and M is 2.
7. The metal complex of formula (I) according to claim 1, wherein in the group of formula (II),
G1is substituted or unsubstituted C1-8Alkyl, phenyl, furyl or thienyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group;
G2is hydrogen, deuterium, C1-4Alkyl radical, C1-4Haloalkyl or C1-4A deuterated alkyl group;
G3is substituted or unsubstituted C1-8Alkyl, the substituents of which are selected from deuterium, halogen or C3-6A cycloalkyl group;
n is 1.
8. The metal complex represented by the formula (I) according to claim 1, wherein L is selected from one of the following groups L5-1 to 43:
9. the metal complex of formula (I) according to claim 1, wherein the metal complex is selected from the group consisting of:
10. use of a metal complex of formula (I) according to any one of claims 1 to 9 as a luminescent material.
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