CN114644657B - 二价铂配合物 - Google Patents
二价铂配合物 Download PDFInfo
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- CN114644657B CN114644657B CN202011618074.3A CN202011618074A CN114644657B CN 114644657 B CN114644657 B CN 114644657B CN 202011618074 A CN202011618074 A CN 202011618074A CN 114644657 B CN114644657 B CN 114644657B
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- substituted
- platinum complex
- carbon atoms
- unsubstituted
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000005841 biaryl group Chemical group 0.000 claims 2
- 239000002019 doping agent Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 27
- 238000003786 synthesis reaction Methods 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000003446 ligand Substances 0.000 abstract description 5
- CAMRHYBKQTWSCM-UHFFFAOYSA-N oxocyanamide Chemical compound O=NC#N CAMRHYBKQTWSCM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 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 8
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 229910019029 PtCl4 Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 cyano, sulfonyl Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000004404 heteroalkyl group Chemical group 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000005104 aryl silyl group Chemical group 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Crystallography & Structural Chemistry (AREA)
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- Optics & Photonics (AREA)
Abstract
本发明涉及二价铂配合物,其结构如式(I)所示。该配合物具有明亮的绿光发射波长,可在OLED有机电致发光材料领域应用。本发明通过结构设计,能提高磷光材料的重原子效应,增强自旋耦合,能实现T1‑S0高效转化,从而得到高效的发光效率。同时ONCN四齿配体的铂配合物分子具有合成步骤简单,配位较为容易等优点,同时较多的可修饰位点,可进行PL发光波长以及热稳定性的调整。所含的咔唑基团增加的位阻,能有效降低分子间的聚集作用,避免形成激基复合物,进一步提高色纯度以及发光效率。
Description
技术领域
本发明涉及OLED材料领域,特别是涉及一类含咔唑的二价铂配合物。
背景技术
有机发光二极管(Organic Light-Emitting Diode,OLED)具有自发光、广视角、几乎无穷高的对比度、较低耗电、极高反应速度以及潜在的柔性可折叠等优点,近二十年来受到广泛的关注与研究。自1979年在实验室中由美籍华裔教授邓青云(Ching W.Tang)发现开始,1998年S.R.Forrest等人又发现有机金属配合物因其强自旋轨道耦合(SOC)可以实现快速的系间窜越(ISC)和长寿命的磷光衰变。并且研究表明磷光材料在发光过程中可以充分利用单线态和三线态激子的能量,提高配合物的发光效率从而在OLED中理论上实现达100%的内部量子效率,尤其对Ir(I)配合物的研究居多,是目前业界使用比较广的发光材料。然而,稀土金属Ir价格昂贵、且污染较大,阻碍了它们在大量生产中的应用。因此,我们极需开发出廉价的金属配合物。金属铂配合物因为其平面性导致的优异材料稳定性,结构具有的很强可修饰性以及其金属价格廉价于铱,使得的近年来也得到了科研产业方面的诸多关注,产业化进程也趋向于成熟。即便如此,目前产业界依然迫切的需要简单高效率和长使用寿命的发光材料。ONCN四齿配体的铂配合物分子具有合成步骤简单,具有较多的可修饰位点,可改进空间极大。
发明内容
针对现有技术存在的上述问题,本发明提供了一类含功能基团的ONCN四齿配体的铂配合物发光材料,该材料能提高磷光材料的重原子效应,从而提高在发光过程中对单线态和三线态激子的能量的利用率。功能集团通过不同位点的连接改进了材料的热稳定性,为该类材料进一步产业化提供了可能性。
该铂配合物应用于有机发光二极管中体现了良好的热稳定性能,光电性能和器件寿命。
该类二价铂配合物,结构式如式(I)所示:
R1-R24中的R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,其余位点和A0独立的选自氢,氘,卤素,取代或未取代的具有1-20个碳原子的烷基,取代或未取代的具有3-20个环碳原子的环烷基,取代或未取代的具有1-20个碳原子的杂烷基,取代或未取代的具有7-30个碳原子的芳烷基,取代或未取代的具有1-20个碳原子的烷氧基,取代或未取代的具有6-30个碳原子的芳氧基,取代或未取代的具有2-20个碳原子的烯基,取代或未取代的具有6-30个碳原子的芳基,取代或未取代的具有3-30个碳原子的杂芳基,取代或未取代的具有3-20个碳原子的烷硅基,取代或未取代的具有6-20个碳原子的芳基硅烷基,取代或未取代的具有0-20个碳原子的胺基,酰基,羰基,羧酸基,酯基,氰基,硫基,亚磺酰基,磺酰基,膦基,或者相邻R1-R24相互通过共价键连接成环;
Ar选自取代或未取代的具有1-20个碳原子的烷基,取代或未取代的具有3-20个环碳原子的环烷基,取代或未取代的具有1-20个碳原子的杂烷基,取代或未取代的具有7-30个碳原子的芳烷基,取代或未取代的具有1-20个碳原子的烷氧基,取代或未取代的具有6-30个碳原子的芳氧基,取代或未取代的具有2-20个碳原子的烯基,取代或未取代的具有6-30个碳原子的芳基,取代或未取代的具有3-30个碳原子的杂芳基,取代或未取代的具有3-20个碳原子的烷硅基,取代或未取代的具有6-20个碳原子的芳基硅烷基;
所述杂烷基或杂芳基中的杂原子为N、S、O;
所述取代为被氘、卤素、氨基、硝基、氰基或C1-C4烷基所取代。
优选的:R1-R24中的R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,其余位点和A0独立的选自氢、氘、卤素、含1-10个C原子的烷氧基、氰基、苯乙烯基、芳氧基、二芳胺基、含1-10个C原子的饱和烷基、含2-8个C原子的不饱和烷基、含5-20个C原子取代的或未取代的芳基、含5-20个C原子取代的或未取代的杂芳基、或者相邻R1-R24相互通过共价键连接成环。
Ar选自取代或未取代的具有6-30个碳原子的并芳基衍生物或并杂芳基衍生物、取代或未取代的具有3-30个碳原子的联芳基衍生物或联杂芳基衍生物。
进一步优选的:
R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,R1-R24其余位点中除R17,R19为C1-C4基以外都为氢,并且A0为氢。
Ar选自取代或未取代的具有5-30个碳原子的芳基、杂芳基,苯并杂芳基。
优选:R17,R19为异丁基,Ar选自取代或未取代的具有苯基、五元或六元杂芳基,苯并杂芳基,所述杂芳基中的杂原子为N、O,所述取代为被氘、卤素或C1-C4烷基所取代。
以下列出按照本发明的铂金属配合物,但不限于所列举的结构:
上述配合物的前体,结构如下式(II)所示:
其中R1-R24、A0、Ar如前所述。
本发明的二价铂配合物作为发光层的磷光掺杂材料在OLED中的应用。
本发明通过结构设计,提高了材料的稳定性,器件效率以及使用寿命。
该类化合物合成步骤简单,很容易具备成熟工艺。
该类结构具有较多的可修饰位点,所含的咔唑基团增加的位阻,能有效降低分子间的聚集作用。
该类化合物可通过功能基团在不同位点的连接,改善分子空间构型,提高色纯度以及发光效率。
本发明的二价铂配合物具有明亮的绿光发射波长,可在OLED有机电致发光材料领域应用。本发明通过结构设计,能提高磷光材料的重原子效应,增强自旋耦合,能实现T1-S0高效转化,从而得到高效的发光效率。同时ONCN四齿配体的铂配合物分子具有合成步骤简单,配位较为容易等优点,同时较多的可修饰位点,可进行PL发光波长以及热稳定性的调整。所含的咔唑基团增加的位阻,能有效降低分子间的聚集作用,避免形成激基复合物,进一步提高色纯度以及发光效率。
本发明中的有机金属配合物具有高荧光量子效率,良好的热稳定性及低淬灭常数,可以制造高发光效率的绿光OLED器件。
附图说明
图1本发明器件结构图。
具体实施方式
下面结合附图和实施例对本发明做进一步的限定。
下面所用的原料均为市售。
实施例1:
结构1化合物的合成(1a,参考CN110872325A,1d为订购物料)
中间体1c的合成
取2L三口瓶,投入1a(60.0g,101mmol)、1b(30.0g,202mmol)、Pd(PPh3)4(5.90g,5mmol)、NaOH(8.2mg,202mmol)和二氧六环/水(1.2L/240ml),氮气保护,55℃搅拌反应12h。反应结束后,先旋干大部分溶剂,加水,DCM萃取2次,拌硅胶旋干用(Hex:EA=10:1)过硅胶柱。得58g白色固体。氢谱数据如下:
1H NMR(400MHz,CDCl3)δ8.69(s,1H),8.61(d,J=5.3Hz,1H),8.23(d,J=7.8Hz,1H),8.12–8.01(m,3H),7.91(d,J=1.4Hz,1H),7.85(d,J=1.7Hz,1H),7.62(s,1H),7.55(s,3H),7.47–7.39(m,1H),7.30–7.26(m,1H),7.16(s,1H),7.06(d,J=8.1Hz,1H),3.92(s,3H),1.41(s,18H).
中间体1e的合成
取250ml单口瓶,投入1c(8.0g,19.9mmol)、1d(6.14g,21.4mmol)、Pd132(0.303g,0.42mmol)、K2CO3(5.9g,42.7mmol)、和THF/水(80ml/16ml),氮气保护,70℃反应12h。反应结束后,先旋干大部分溶剂,加水,EA萃取2次,拌硅胶旋干,用(Hex:EA=6:1)过硅胶柱,得9.7g白色固体。氢谱数据如下:
1H NMR(400MHz,CDCl3)δ8.76(d,J=4.1Hz,2H),8.34–8.23(m,2H),8.20(d,J=7.8Hz,1H),8.13(d,J=7.8Hz,1H),8.10–8.01(m,3H),7.96(s,1H),7.73–7.55(m,10H),7.55–7.38(m,5H),7.34(t,J=6.4Hz,1H),7.15(t,J=7.5Hz,1H),7.07(d,J=8.2Hz,1H),3.93(s,3H),1.44(s,18H).
中间体1f的合成
取500ml单口瓶,投入1e(8.5g,11.06mmol)、吡啶盐酸盐(90g)和9mL邻二氯苯,氮气保护,200度反应6h。反应结束后,用二氯甲烷萃取两次,旋干拌硅胶过柱(Hex:EA=6:1)。
所得粗品用甲醇打浆。得到淡黄色固体8.3g。氢谱数据如下:
1H NMR(400MHz,CDCl3)δ8.74(d,J=4.8Hz,1H),8.64(s,1H),8.25(d,J=8.1Hz,1H),8.17(dd,J=12.1,8.0Hz,2H),8.07(t,J=9.5Hz,3H),7.95(d,J=8.1Hz,1H),7.92(d,J=1.1Hz,1H),7.73–7.64(m,3H),7.64–7.57(m,5H),7.56–7.50(m,3H),7.50–7.39(m,3H),7.39–7.28(m,2H),7.12–7.04(m,1H),6.97(t,J=7.0Hz,1H),1.43(s,18H).
终产物结构1所示化合物的合成
取500ml单口瓶,投入1f(2.0g,2.65mmol)、K2PtCl4(1.32g,3.18mmol)、TBAB(85mg,0.265mmol)和乙酸(200mL),氮气保护,130度反应48h。反应结束后,加入过量的去离子水,固体析出,抽滤,固体用二氯甲烷溶解,旋干拌硅胶过柱(DCM)。得到黄色固体1.6g。氢谱数据如下:
1H NMR(400MHz,CDCl3)δ8.89(d,J=5.9Hz,1H),8.21–8.01(m,3H),7.88(d,J=7.7Hz,1H),7.74–7.47(m,12H),7.47–7.34(m,3H),7.34–7.28(m,3H),7.24(d,J=5.6Hz,2H),7.07(t,J=7.5Hz,1H),6.52(t,J=7.4Hz,1H),1.45(s,18H).
实施例2:结构26化合物的合成(26a为订购物料)
中间体26b的合成
取250ml单口瓶,投入1c(8.0g,19.9mmol)、26a(8.5g,21.4mmol)、Pd132(0.303g,0.42mmol)、K2CO3(5.9g,42.7mmol)、和THF/水(80ml/16ml),氮气保护,70℃反应12h。反应结束后,先旋干大部分溶剂,加水,EA萃取2次,拌硅胶旋干,用(Hex:EA=6:1)过硅胶柱,得11.08g白色固体。氢谱数据如下:
1H NMR(400MHz,Chloroform-d)δ8.67(d,J=4.5Hz,1H),8.22–8.17(m,3H),8.17–8.08(m,3H),7.95–7.86(m,4H),7.72(dd,J=6.8,2.4Hz,1H),7.69–7.59(m,2H),7.53–7.27(m,10H),7.15(ddd,J=8.7,7.5,1.2Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,36H).
中间体26c的合成
取500ml单口瓶,投入26b(9.74g,11.06mmol)、吡啶盐酸盐(90g)和9mL邻二氯苯,氮气保护,200度反应6h。反应结束后,用二氯甲烷萃取两次,旋干拌硅胶过柱(Hex:EA=6:1)。所得粗品用甲醇打浆。得到淡黄色固体8.3g。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ9.18–9.11(m,1H),8.26–8.09(m,5H),7.94(dd,J=8.2,1.2Hz,1H),7.74(d,J=2.1Hz,1H),7.68–7.62(m,3H),7.60–7.52(m,2H),7.51–7.44(m,3H),7.40–7.26(m,9H),7.17(d,J=6.7Hz,2H),7.09(ddd,J=8.4,7.5,1.2Hz,1H),1.36(d,J=2.9Hz,38H).
终产物结构26所示化合物的合成
取500ml单口瓶,投入26c(2.3g,2.65mmol)、K2PtCl4(1.32g,3.18mmol)、TBAB(85mg,0.265mmol)和乙酸(200mL),氮气保护,130度反应48h。反应结束后,加入过量的去离子水,固体析出,抽滤,固体用二氯甲烷溶解,旋干拌硅胶过柱(DCM)。得到黄色固体1.8g。氢谱数据如下:
1H NMR(400MHz,CDCl3)δ8.89(d,J=5.9Hz,1H),8.21–8.01(m,3H),7.88(d,J=7.7Hz,1H),7.74–7.47(m,12H),7.47–7.34(m,3H),7.34–7.28(m,3H),7.24(d,J=5.6Hz,2H),7.07(t,J=7.5Hz,1H),6.52(t,J=7.4Hz,1H),1.45(s,18H).
实施例3:结构36化合物的合成(36a为订购物料)
中间体36c的合成
36a在干燥的500ml双颈烧瓶中(14.7g,50mmol),加入36b(11.8g,50mmol)、甲苯(120mL),加入乙醇(60mL)和2mol/L碳酸钾溶液(60mL),先超声5-10分钟,然后迅速搅拌氮气5分钟,迅速加入催化剂四(三苯基膦)钯.(1.8g,1.5mmol),大量通氮气10分钟。加热至100℃,搅拌12小时,处理时先提取,旋干,用石油醚和二氯甲烷柱层析,得到白色固体产物14.5g,收率为90%。氢谱数据如下:
1H NMR(400MHz,Chloroform-d)δ9.54(s,1H),8.37(dd,J=4.0,2.2Hz,1H),8.17–8.10(m,2H),7.94(dd,J=7.5,2.2Hz,1H),7.56(s,1H),7.55–7.48(m,2H),7.46(dd,J=7.5,3.9Hz,1H),7.34(td,J=7.4,1.3Hz,1H),7.28–7.19(m,1H).
中间体36d的合成
36c在干燥的500ml双颈烧瓶中(14.5g,45mmol),加入1a(28.7g,50mmol)、甲苯(120mL),加入乙醇(60mL)和2mol/L碳酸钾溶液(60mL),先超声5-10分钟,然后迅速搅拌氮气5分钟,迅速加入催化剂四(三苯基膦)钯.(1.8g,1.5mmol),大量通氮气10分钟。加热至100℃,搅拌12小时,处理时先提取,旋干,用石油醚和二氯甲烷柱层析,得到白色固体产物10.2g,收率为78%。氢谱数据如下:
1H NMR(400MHz,Chloroform-d)δ9.54(s,1H),8.71(dd,J=4.1,2.2Hz,1H),8.19(t,J=2.0Hz,1H),8.17–8.08(m,2H),8.02(dd,J=1.9,0.7Hz,1H),7.96–7.87(m,4H),7.80(ddd,J=8.5,1.9,1.2Hz,1H),7.67(t,J=8.6Hz,1H),7.57(d,J=8.3Hz,1H),7.54–7.48(m,2H),7.47–7.32(m,7H),7.24(ddd,J=7.9,7.3,1.6Hz,1H),7.15(ddd,J=8.7,7.5,1.2Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).
中间体36f的合成
在250ml三口瓶中,加入36d(5.0g,1.0eq)、36e(5.7g,3.0eq)、Cu(230mg,0.5eq)、CuI(688mg,0.5eq)、1,10-菲啰啉(1.30g,1.0eq)及碳酸铯(7.06g,3.0eq),100ml无水二甲苯作反应溶剂,氮气保护,油浴温度160℃反应3d后冷却至室温,反应液以EA作淋洗剂直接抽滤除去无机盐后拌硅胶柱层析(层析液hex:EA=8:1),收集得到黄色荧光产物点3.9g。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.71(dd,J=4.1,2.2Hz,1H),8.24(dd,J=1.9,0.7Hz,1H),8.22–8.08(m,5H),8.02(ddt,J=8.9,1.3,0.5Hz,1H),7.97–7.85(m,5H),7.84–7.77(m,2H),7.71–7.62(m,4H),7.59–7.53(m,1H),7.53–7.27(m,13H),7.15(ddd,J=8.7,7.5,1.2Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).
中间体36g的合成
在100ml单口瓶中,加入36f(3.15g),吡啶盐酸盐(30.0g)及邻二氯苯(3.0ml),氮气保护,油浴温度200℃反应8h后冷却至室温。用大量水溶解并用DCM萃取三次,有机相旋干拌硅胶柱层析(层析液hex:EA=10:1),得淡黄色产物2.8g。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.71(dd,J=4.1,2.2Hz,1H),8.24(dd,J=1.9,0.7Hz,1H),8.21–8.08(m,5H),8.06–7.97(m,2H),7.97–7.77(m,6H),7.71–7.62(m,4H),7.59–7.53(m,1H),7.53–7.44(m,5H),7.44–7.20(m,8H),7.03–6.94(m,2H),1.35(s,18H).
终产物结构36所示化合物的合成
取250ml单口瓶,投入36g(105mg,0.124mmol)、K2PtCl4(70mg,0.167mmol)、18冠6醚(6mg,0.012mmol)和乙酸(5mL),氮气保护,130度反应48h。反应结束后,加入过量的去离子水,固体析出,抽滤,固体用二氯甲烷溶解,旋干拌硅胶过柱(Hex:DCM:EA=20:20:1)。过柱后产品用二氯甲烷:正己烷=1:4重结晶。得到红色固体85mg。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.84(dd,J=5.4,2.3Hz,1H),8.21(d,J=1.8Hz,1H),8.17–7.99(m,5H),7.94(dd,J=8.1,1.2Hz,1H),7.81(t,J=1.2Hz,1H),7.76–7.62(m,6H),7.58–7.43(m,12H),7.42–7.26(m,8H),7.25–7.15(m,2H),7.09(ddd,J=8.5,7.5,1.2Hz,1H),1.35(s,18H).
实施例4:结构53化合物的合成(53a为订购物料)
中间体53c的合成:
53a在干燥的500ml双颈烧瓶中(14.7g,50mmol),加入53b(11.8g,50mmol)、甲苯(120mL),加入乙醇(60mL)和2mol/L碳酸钾溶液(60mL),先超声5-10分钟,然后迅速搅拌氮气5分钟,迅速加入催化剂四(三苯基膦)钯.(1.8g,1.5mmol),大量通氮气10分钟。加热至100℃,搅拌12小时,处理时先提取,旋干,用石油醚和二氯甲烷柱层析,得到白色固体产物14.5g,收率为90%。氢谱数据如下:
1H NMR(400MHz,Chloroform-d)δ9.72(s,1H),8.37(dd,J=4.0,2.2Hz,1H),8.19–8.13(m,1H),8.13–8.06(m,1H),7.91(dd,J=7.4,2.3Hz,1H),7.83(d,J=1.9Hz,1H),7.71(dd,J=8.1,2.0Hz,1H),7.55–7.42(m,2H),7.34(td,J=7.4,1.3Hz,1H),7.24(ddd,J=7.9,7.3,1.6Hz,1H).
中间体53d的合成
53c在干燥的500ml双颈烧瓶中(14.5g,45mmol),加入1a(28.7g,50mmol)、甲苯(120mL),加入乙醇(60mL)和2mol/L碳酸钾溶液(60mL),先超声5-10分钟,然后迅速搅拌氮气5分钟,迅速加入催化剂四(三苯基膦)钯.(1.8g,1.5mmol),大量通氮气10分钟。加热至100℃,搅拌12小时,处理时先提取,旋干,用石油醚和二氯甲烷柱层析,得到白色固体产物10.2g,收率为78%。氢谱数据如下:
1H NMR(400MHz,Chloroform-d)δ9.72(s,1H),8.71(dd,J=4.1,2.2Hz,1H),8.22–8.06(m,5H),7.97–7.86(m,5H),7.84–7.74(m,2H),7.71–7.60(m,2H),7.55–7.47(m,2H),7.45–7.30(m,6H),7.24(ddd,J=7.9,7.3,1.6Hz,1H),7.15(ddd,J=8.7,7.5,1.2Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).
中间体53f的合成
在250ml三口瓶中,加入53d(5.0g,1.0eq)、53e(7.0g,3.0eq)、Cu(230mg,0.5eq)、CuI(688mg,0.5eq)、1,10-菲啰啉(1.30g,1.0eq)及碳酸铯(7.06g,3.0eq),100ml无水二甲苯作反应溶剂,氮气保护,油浴温度160℃反应3d后冷却至室温,反应液以EA作淋洗剂直接抽滤除去无机盐后拌硅胶柱层析(层析液hex:EA=8:1),收集得到黄色荧光产物点4.1g。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.71(dd,J=4.1,2.2Hz,1H),8.40–8.28(m,5H),8.28–8.16(m,3H),8.11(d,J=2.2Hz,1H),7.97–7.85(m,5H),7.85–7.77(m,4H),7.67(t,J=8.5Hz,1H),7.57–7.35(m,14H),7.31(ddd,J=7.9,7.2,1.6Hz,1H),7.15(ddd,J=8.7,7.5,1.2Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).
中间体53g的合成
在100ml单口瓶中,加入53f(3.40g),吡啶盐酸盐(30.0g)及邻二氯苯(3.0ml),氮气保护,油浴温度200℃反应8h后冷却至室温。用大量水溶解并用DCM萃取三次,有机相旋干拌硅胶柱层析(层析液hex:EA=10:1),得淡黄色产物2.9g。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.71(dd,J=4.1,2.2Hz,1H),8.40–8.28(m,5H),8.28–8.16(m,4H),8.11(d,J=2.2Hz,1H),7.99(dd,J=8.7,1.2Hz,1H),7.96–7.73(m,8H),7.67(t,J=8.5Hz,1H),7.56–7.37(m,13H),7.36–7.20(m,2H),7.03–6.94(m,2H),1.35(s,18H).
终产物结构53所示化合物的合成
取250ml单口瓶,投入53g(115mg,0.124mmol)、K2PtCl4(70mg,0.167mmol)、18冠6醚(6mg,0.012mmol)和乙酸(5mL),氮气保护,130度反应48h。反应结束后,加入过量的去离子水,固体析出,抽滤,固体用二氯甲烷溶解,旋干拌硅胶过柱(Hex:DCM:EA=20:20:1)。过柱后产品用二氯甲烷:正己烷=1:4重结晶。得到红色固体85mg。氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ8.84(dd,J=6.0,1.8Hz,1H),8.40–8.28(m,5H),8.28–8.18(m,2H),8.15–8.10(m,1H),8.04–7.99(m,1H),7.94(dd,J=8.1,1.2Hz,1H),7.80–7.61(m,7H),7.59–7.42(m,13H),7.39–7.26(m,5H),7.25–7.15(m,2H),7.09(ddd,J=8.5,7.5,1.2Hz,1H),1.35(s,18H).
化合物发光性质:
下面是本发明化合物的应用实例。
器件制备方式:
首先,将透明导电ITO玻璃基板10(上面带有阳极20)依次经:洗涤剂溶液和去离子水,乙醇,丙酮,去离子水洗净,再用氧等离子处理300秒。
然后,在ITO上蒸渡3nm厚的HATCN作为空穴注入层30。
然后,蒸渡化合物TAPC,形成50nm厚的空穴传输层40。
然后,在空穴传输层上蒸渡7nm厚的客体配合物(9%)与主体TCTA(91%)作为发光层50。
然后,在空穴传输层上蒸渡3nm厚的客体配合物(9%)与主体TCTA(91%)作为发光层60。
然后,在发光层上蒸渡50nm厚的TmPyPb作为空穴阻挡层70。
最后,蒸渡0.8nm LiF为电子注入层80和100nm Al作为器件阴极90。
器件结构如图1所示
器件中所用化合物的结构式如下:
器件结果:
比较例1及比较例2中的有机电致发光器件在20mA/cm2电流密度下的器件性能列于表1:
表1
本发明中的有机金属配合物在保持了高量子效率的良好的同时,略微降低了器件的驱动电压,提高了发光效率。但是对比比较例的LT95,实施例器件寿命明显有着质的提升。该系列器件数据表明,此类二价铂配合物做磷光发光配体材料时,可以制造出高发光效率的OLED器件并且可以达到非常好的寿命。
上述多种实施方案仅作为示例,不用于限制本发明范围。在不偏离本发明精神的前提下,本发明中的多种材料和结构可以用其它材料和结构替代。应当理解,本领域的技术人员无需创造性的劳动就可以根据本发明的思路做出许多修改和变化。因此,技术人员在现有技术基础上通过分析、推理或者部分研究可以得到的技术方案,均应在本申请所限制的保护范围内。
Claims (9)
1.二价铂配合物,结构式如式(I)所示:
其中R1-R24中的R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,其余位点和A0独立的选自氢,氘,卤素,取代或未取代的具有1-20个碳原子的烷基,取代或未取代的具有3-20个环碳原子的环烷基,氰基;
Ar选自取代或未取代的具有6-30个碳原子的芳基,取代或未取代的具有3-30个碳原子的杂芳基;
所述杂芳基中的杂原子为N、S、O;
所述取代为被氘、卤素、氰基或C1-C4烷基所取代;
且二价铂配合物不为下述结构:
2.根据权利要求1所述的二价铂配合物,所述R1-R24中的R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,其余位点和A0独立的选自氢、氘、卤素、含1-10个C原子的饱和烷基。
3.根据权利要求2所述的二价铂配合物,Ar选自取代或未取代的具有6-30个碳原子的并芳基或联芳基、取代或未取代的具有3-30个碳原子的并杂芳基或联杂芳基。
4.根据权利要求3所述的二价铂配合物,所述R1-R24中的R1-R6的其中一个位点与R7-R10的其中一个位点以C-C键连接,其余位点中除R17,R19为C1-C4基以外都为氢,并且A0为氢。
5.根据权利要求1所述的二价铂配合物,其中Ar选自取代或未取代的具有6-30个碳原子的芳基、取代或未取代的具有5-30个碳原子的杂芳基或苯并杂芳基。
6.根据权利要求5所述的二价铂配合物,其中R17,R19为异丁基,Ar选自取代或未取代的苯基、五元或六元杂芳基、苯并杂芳基,所述杂芳基中的杂原子为N、O,所述取代为被氘、卤素或C1-C4烷基所取代。
7.根据权利要求1所述的二价铂配合物,为如下所示结构之一:
8.权利要求1-7任一所述的二价铂配合物的前体,结构如下式所示:
其中R1-R24、A0、Ar如前所述。
9.权利要求1-7任一所述的二价铂配合物作为发光层的磷光掺杂材料在OLED中的应用。
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