CN107849062B - 用于oled应用的金络合物 - Google Patents
用于oled应用的金络合物 Download PDFInfo
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- CN107849062B CN107849062B CN201680034413.9A CN201680034413A CN107849062B CN 107849062 B CN107849062 B CN 107849062B CN 201680034413 A CN201680034413 A CN 201680034413A CN 107849062 B CN107849062 B CN 107849062B
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- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical compound [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- -1 cyano, carboxy Chemical group 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 16
- 239000003446 ligand Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
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- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
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- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 6
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- 125000000623 heterocyclic group Chemical group 0.000 description 6
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- 239000013058 crude material Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 150000003573 thiols Chemical class 0.000 description 5
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- 239000010931 gold Substances 0.000 description 4
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- 125000005504 styryl group Chemical group 0.000 description 4
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- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
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- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
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- 125000003107 substituted aryl group Chemical group 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 229910016460 CzSi Inorganic materials 0.000 description 2
- 101150091653 PYD2 gene Proteins 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
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- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- XNCMQRWVMWLODV-UHFFFAOYSA-N 1-phenylbenzimidazole Chemical compound C1=NC2=CC=CC=C2N1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- KUPTUOSPHDZOOR-UHFFFAOYSA-N 2,4-ditert-butyl-6-diphenylphosphanylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1O KUPTUOSPHDZOOR-UHFFFAOYSA-N 0.000 description 1
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- UKWMNFHGYXRSFQ-UHFFFAOYSA-N 5,7-dimethylquinolin-8-ol Chemical compound C1=CC=NC2=C(O)C(C)=CC(C)=C21 UKWMNFHGYXRSFQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
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- 241000764238 Isis Species 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- PANOCYXIFXLORZ-UHFFFAOYSA-N diphenyl-(4-triphenylsilylphenyl)phosphane Chemical compound C1=CC=CC=C1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 PANOCYXIFXLORZ-UHFFFAOYSA-N 0.000 description 1
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Images
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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/12—Gold compounds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
本发明描述显示高发射量子效率和在热分解过程稳定的金(III)发射体。可从这些发射体制造高性能OLED。
Description
技术领域
本公开涉及一类金发射体、其制备及其在有机发光二极管(OLED)中的应用。
发明背景
一直有关注研究用于OLED应用的发光材料,无论是发现适合掺杂剂材料还是优化装置结构,以实现高量子效率、长装置寿命或颜色调节。Ir(III)和Pt(II)络合物在研究领域占主导。它们因优异的发光量子产率和稳定性而被高度认可。
为了具有这些合乎需要的性质,除选择金属离子以外,配位体的结构设计起决定作用。一般做法是使用多齿环金属化配位体。这些多齿配位体通常包含强场供体原子,如C-或O-,以去除低位非发射金属中心(MC)激发态。同时,有多齿配位体而非单齿配位体赋予的螯合效应,这可给予络合物热稳定性。
在过去二十年里,对发光金(III)化合物的研究高涨。发光金(III)络合物存在。但结构设计很大依赖伴有辅助强σ-供体(通常为碳阴离子)的环金属化三齿络合物。只有这种金(III)络合物已用于OLED装置。已通过这些络合物的溶液量子效率获得相对少数量的高性能装置。然而,金(III)中心和辅助单齿配位体之间的相对较弱结合力可影响这些OLED的长期稳定性。
发明概述
本文主题涉及具有高溶液发射量子效率的金(III)发射体及其在OLED中的应用。本文所述金(III)发射体大大改善用于OLED制造的金(III)络合物的发射量子和稳定性。
在一个实施方案中,金(III)基发射体为具有结构I的化学结构的金属络合物:
结构I
其中R1-R8独立为氢、卤素、羟基、未取代烷基、经取代烷基、烷基氨基、环烷基、未取代芳基、经取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰氨基、芳烷基、氰基、羧基、硫醇(thio)、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。R1-R8中任何相邻的R基团对可独立与结构I中所示苯基环中的2或4个碳原子形成5-8元环;并且为发射起始(emission turn on)基团。
本文主题也提供从结构I的金(III)发射体制造的装置。
附图简述
图201:发射体100的合成方案。
图202:102的ORTEP图,椭球体以30%概率水平显示。
图203:104的ORTEP图,椭球体以30%概率水平显示。
图204:107的ORTEP图,椭球体以30%概率水平显示。
图205:109的ORTEP图,椭球体以30%概率水平显示。
图206:发射体103、105、107、108和109的循环伏安图。
图207:发射体102的TGA温谱图。
图208:发射体103的TGA温谱图。
图209:发射体107的TGA温谱图。
图210:发射体101的发射光谱。
图211:发射体102的发射光谱。
图212:通过发射体102制造的VDOLED和SPOLED的EL光谱。
图213:通过发射体102制造的VDOLED和SPOLED的EQE亮度特性。
发明详述
定义
为了帮助理解本文公开主题,以下定义本文所用一些术语、缩写或其它简写。未定义的任何术语、缩写或其它简写应理解为具有与本申请的提交同时期本领域的技术人员使用的普通含义。
“氨基”指可任选经取代的伯胺、仲胺或叔胺。具体包括作为杂环成员的仲或叔胺氮原子。也具体包括例如由酰基部分取代的仲或叔氨基。氨基的一些非限制实例包括-NR’R”,其中各R’和R”独立为H、烷基、芳基、芳烷基、烷芳基、环烷基、酰基、杂烷基、杂芳基或杂环基。
“烷基”指包含碳和氢且可以为支链或直链的完全饱和无环单价基团。烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正庚基、正己基、正辛基和正癸基。
“烷基氨基”指基团-NHR或-NR2,其中各R独立为烷基。烷基氨基的代表性实例包括但不限于甲基氨基、(1-甲基乙基)氨基、甲基氨基、二甲基氨基、甲基乙基氨基和二(1-甲基乙基)氨基。
术语“羟基烷基”指用一个或多个羟基取代的本文限定的烷基,优选一、二或三个羟基。羟基烷基的代表性实例包括但不限于羟基甲基、2-羟基乙基、2-羟基丙基、3-羟基丙基、1-(羟基甲基)-2-甲基丙基、2-羟基丁基、3-羟基丁基、4-羟基丁基、2,3-二羟基丙基、2-羟基-1-羟基甲基乙基、2,3-二羟基丁基、3,4-二羟基丁基和2-(羟基甲基)-3-羟基-丙基,优选2-羟基乙基、2,3-二羟基丙基和1-(羟基甲基)2-羟基乙基。
本文所用术语“烷氧基”指基团-ORx。示例性烷氧基包括但不限于甲氧基、乙氧基和丙氧基。
“芳基”指任选取代的碳环芳族基团。在一些实施方案中,芳基包括苯基、联苯基、萘基、经取代苯基、经取代联苯基或经取代萘基。在其它实施方案中,芳基为苯基或经取代苯基。
“芳烷基”指用芳基取代的烷基。芳烷基的一些非限制实例包括苄基和苯乙基。
“酰基”指式-C(=O)H、-C(=O)-烷基、-C(=O)-芳基、-C(=O)-芳烷基或-C(=O)-烷芳基的单价基团。
“卤素”指氟、氯、溴和碘。
“苯乙烯基”指从苯乙烯衍生的单价基团C6H5-CH=CH-。
本文所用描述化合物或化学部分的“经取代”指那种化合物或化学部分的至少一个氢原子被第二化学部分取代。取代基的非限制实例为本文公开示例性化合物和实施方案中发现的那些取代基,以及卤素;烷基;杂烷基;烯基;炔基;芳基;杂芳基;羟基;烷氧基;氨基;硝基;硫醇;硫醚;亚胺;氰基;酰氨基;膦酸基;膦;羧基;硫代羰基;磺酰基;磺酰胺;酮;醛;酯;氧代;卤代烷基(例如,三氟甲基);可以为单环或稠合或非稠合多环的碳环环烷基(例如,环丙基、环丁基、环戊基或环己基),或可以为单环或稠合或非稠合多环的杂环烷基(例如,吡咯烷基、哌啶基、哌嗪基、吗啉基或噻嗪基);碳环或杂环、单环或稠合或非稠合多环芳基(例如,苯基、萘基、吡咯基、吲哚基、呋喃基、噻吩基、咪唑基、噁唑基、异噁唑基、噻唑基、三唑基、四唑基、吡唑基、吡啶基、喹啉基、异喹啉基、吖啶基、吡嗪基、哒嗪基、嘧啶基、苯并咪唑基、苯并噻吩基或苯并呋喃基);氨基(伯、仲或叔);o-低级烷基;o-芳基,芳基;芳基-低级烷基;-CO2CH3;-CONH2;-OCH2CONH2;-NH2;-SO2NH2;-OCHF2;-CF3;-OCF3;-NH(烷基);-N(烷基)2;-NH(芳基);-N(烷基)(芳基);-N(芳基)2;-CHO;-CO(烷基);-CO(芳基);-CO2(烷基);和-CO2(芳基);这些部分也可任选由稠环结构或桥(例如,-OCH2O-)取代。这些取代基可任选进一步被选自这些基团的取代基取代。除非另外说明,本文公开的所有化学基团均可经取代。例如,本文所述“经取代”烷基、烯基、炔基、芳基、烃基或杂环部分为被烃基部分、经取代烃基部分、杂原子或杂环取代的部分。另外,取代基可包括其中碳原子被杂原子取代的部分,杂原子如氮、氧、硅、磷、硼、硫或卤素原子。这些取代基可包括卤素、杂环、烷氧基、烯氧基、炔氧基、芳氧基、羟基、受保护羟基、酮基、酰基、酰氧基、硝基、氨基、酰氨基、氰基、硫醇、缩酮、缩醛、酯和醚。
金(III)发射体
在一个方面,本文主题提供金(III)发射体。在一个实施方案中,本发明提供由结构I表示的有机金属发射体。结构I中的金中心处于+3氧化态,并具有方形平面几何结构。金中心的配位点由两个二齿配位体占据:联苯类型配位体和发射起始单元(发射起始基团)。具有5元稠环特征的联苯类型配位体通过两个金属-碳键配位到金中心。
具有5或6元稠环特征的发射起始单元通过两个金属-氧键或一个金属-氧和一个金属-氮键或一个金属-磷键配位到金中心。重要的是具有此单元,因为发现在无此单元时,具有联苯类型配位体的金(III)络合物在室温在溶液中为非发射性。
在一个实施方案中,发射起始单元包含2至26个碳原子和至少一个氧原子。在另一个实施方案中,发射起始单元包含4至25个碳原子和至少一个氧原子。
联苯类型配位体必须处于-2氧化态,发射起始单元必须处于-1氧化态,以得到总电荷中性发射体。
在一个实施方案中,金(III)发射体具有结构I的化学结构:
结构I
其中R1-R8独立为氢、卤素、羟基、未取代烷基、经取代烷基、烷基氨基、环烷基、未取代芳基、经取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰氨基、芳烷基、氰基、羧基、硫醇(thio)、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。R1-R8中每对相邻R基团可独立与结构I中所示苯基环中的2或4个碳原子形成5-8元环;为发射起始基团。
在一个实施方案中,R1-R8独立为氢、卤素、羟基、包含1至10个碳原子的未取代烷基、包含1至20个碳原子的经取代烷基、包含4至20个碳原子的环烷基、包含6至20个碳原子的未取代芳基、包含6至20个碳原子的经取代芳基、包含1至20个碳原子的酰基、包含1至20个碳原子的烷氧基、包含1至20个碳原子的酰氧基、氨基、硝基、包含1至20个碳原子的酰氨基、包含1至20个碳原子的芳烷基、氰基、包含1至20个碳原子的羧基、硫醇、苯乙烯基、包含1至20个碳原子的氨基羰基、包含1至20个碳原子的氨基甲酰基、包含1至20个碳原子的芳氧基羰基、包含1至20个碳原子的苯氧基羰基或包含1至20个碳原子的烷氧基羰基。
在一个实施方案中,R1、R3、R4、R5、R6和R8为氢,R2和R7独立为氢或包含1至10个碳原子的未取代烷基。
在一个实施方案中,R1、R3、R4、R5、R6和R8为氢,R2和R7独立为氢或叔丁基。
在一个实施方案中,X为氧原子。
在一个实施方案中,发射起始单元为:
在一个实施方案中,发射起始单元为:
在一个实施方案中,发射起始单元为:
在一个实施方案中,发射起始单元为:
在一个实施方案中,X为氮原子。
在一个实施方案中,发射起始单元为:
在一个实施方案中,发射起始单元为:
在一个实施方案中,X为磷原子。
在一个实施方案中,发射起始单元为:
具有结构I的金(III)发射体的某些具体非限制实例显示如下:
制备金(III)发射体
可通过图201中所绘的反应序列制备具有结构I的金(III)发射体。
根据图201,从配位体300通过反应510制备中间体410。随后,利用反应520转化成中间体420。最后,通过反应530从中间体420制备发射体100。
在一个实施方案中,反应510是使配位体300与正丁基锂在适合温度和时间反应,例如在77K反应2小时,然后在室温加入SnBu2Cl2。
在一个实施方案中,反应520是使中间体410与HAuCl4·3H2O在适合溶剂或混合溶剂中反应。
在一个实施方案中,反应530是使中间体420与二质子化发射起始单元在适合溶剂或混合溶剂中反应。
以下实施例说明本发明。除非在以下实施例和在说明书和权利要求中别的地方另外指明,所有份数和百分数均以重量计,所有温度为℃,压力在或接近大气压。
实施例601 - 制备中间体411
在N2下在77 K,将n-BuLi (2.7mL, 6.48mmo)加到溶于30mL无水乙醚的配位体301(1g, 3.21mmol)。立即使反应混合物温热至室温,并搅拌2小时。将溶于3mL无水乙醚的二氯化二丁基锡(0.98g, 3.23mmol)用注射器注入反应混合物。在加入后,浅黄色浑浊溶液变成乳白色。在室温搅拌过夜后,加入H2O,并萃取有机层。去除溶剂得到浅黄色固体。随后用纯己烷柱层析得到纯产物,为白色固体。产率:0.72g (58.3%)。1H NMR (400 MHz, CDCl3): δ7.96 (d, 2H, J = 7.82 Hz) , 7.63 (d, 2H, 118Sn伴生物(satellite), J = 7.82 Hz,JHPt = 35.0 Hz) , 7.40 (t, 2H, J = 7.62 Hz) , 7.28 (d, 2H, J = 7.06 Hz) , 1.58-1.66 (m, 4H) , 1.31 -1.39 (m, 8H) , 0.87 (t, 6H, J = 7.29 Hz)。
实施例602 - 制备中间体412
程序类似于实施例601,不同之处在于用配位体302 (1.4g, 3.31mmol)代替配位体301。产率:0.70g (42.6 %)。1H NMR (400 MHz, CDCl3): δ 7.84 (d, 2H, J = 8.28 Hz), 7.62 (d, 2H, 118Sn伴生物, J = 1.97 Hz, JHPt = 36.1 Hz) , 7.39 (dd, 2H, J =8.25 Hz, J = 2.10 Hz) , 1.64 - 1.69 (m, 4H) , 1.31 - 1.42 (m, 26H) , 0.89 (t,6H, J = 7.31 Hz)。
实施例603 - 制备中间体421
使HAuCl4.3H2O(200mg, 0.508mmol)溶于20mL MeCN。加入中间体411(200mg,0.52mmol)。将混合物加热到80℃,并反应过夜。将灰白色沉淀过滤,并彻底用MeCN和CHCl3洗涤。产率:77mg (38.7%)。
实施例604 - 制备中间体422
程序类似于中间体421,不同之处在于使用中间体412(252mg, 0.507mmol)。产率:128mg (50.5%)。
实施例605 - 制备发射体101
使Na(acac) (10mg, 0.08mmol)溶于最小量EtOH。加入10mL CHCl3。向混合物加入中间体421(30mg, 0.039mmol),并使温度升高到50℃。浑浊溶液过夜变得较澄清。然后在减压下蒸发溶剂。使粗物质重新溶于CHCl3,并通过硅藻土塞过滤。产物在MeOH中沉淀得到白色固体产物。产率:16mg (44.3%)。1H NMR (400 MHz, CDCl3): δ 7.67 (d, 2H, J = 7.69Hz) , 7.32 (d, 2H, J = 7.53 Hz) , 7.19 (t, 2H, J = 7.41 Hz) , 7.00 (t, 2H, J= 7.55 Hz) , 5.52 (s, 1H) , 2.19 (s, 6H) . 对C17H15AuO2计算的元素分析:C, 45.55;H, 3.37; O, 7.14。实验值:C, 46.38; H, 3.50。
实施例606 - 制备发射体102
使K(OPPh2)2N (61mg, 0.130mmol)溶于最小量EtOH。加入10mL CHCl3。向混合物加入中间体421(50mg, 0.065mmol),使温度升高到50℃,并反应2h。将具有一些金属沉积物的无色溶液通过硅藻土塞过滤。然后在减压下蒸发溶剂。产物在MeOH中沉淀得到白色固体产物。在CHCl3/己烷中重结晶得到发射体102,为无色结晶。产率:45mg (45.2%)。MS (FAB) m/z: 765.8 [M+] . 1H NMR (400 MHz, CDCl3): δ 7.84 -7.90 (m, 8H) , 7.72 (d, 2H, J= 7.78 Hz) , 7.38 -7.41 (m, 4H) , 7.33 -7.36 (m, 8H) , 7.27 -7.32 (m, 2H) ,7.17 (t, 2H, J = 7.47 Hz) , 6.98 (t, 2H, J =7.58 Hz) ; 31P NMR (162 MHz,CDCl3): δ 28.8; 13C NMR (150 MHz, CDCl3): δ 121.4, 126.6, 128.2, 128.3 (JCP =13.64 Hz) 128.4, 129.5, 131.1, 131.2, 136.0 (3JCP = 3.24 Hz) , 136.9 (3JCP =3.24 Hz) 148.1, 151.7 . 对C36H28AuNO2P2计算的元素分析:C, 56.48; H, 3.69; N,1.83。实验值:C, 56.45; H, 3.61; N, 1.93。
实施例607 - 制备发射体103
使K2CO3粉末(25mg, 0.18mmol)悬浮于少量EtOH,加到溶于10mL CHCl3的1-(3-羟基苯并[b]噻吩-2-基)乙酮(17.6mg, 0.092mmol)。将混合物加热到50℃,随后加入中间体421(35mg, 0.046mmol)。反应过夜后,过滤黄色悬浮体,并重新溶于THF。通过硅藻土过滤THF溶液。在THF/己烷中重结晶得到发射体103,为黄色固体。产率:22mg (37.1%)。1H NMR(400 MHz, CDCl3): δ 7.84 -7.90 (m, 8H) , 7.72 (d, 2H, J = 7.78 Hz) , 7.35 -7.43 (m, 12H) , 7.27 -7.32 (m, 2H) , 7.17 (t, 2H, J = 7.47 Hz) , 6.98 (t, 2H,J = 7.58 Hz) . 对C22H15AuO2S计算的元素分析:C, 48.9; H, 2.8。实验值:C, 49.06; H,2.80。
实施例608 - 用于发射体104-106的一般步骤
使K2CO3粉末(4eq.)悬浮于EtOH。将其加到溶于CHCl3的R-OH (2eq.)。将混合物加热到50℃经历10分钟,随后加入中间体421(1eq.)。使混合物反应过夜。然后在减压下蒸发溶剂。使粗物质重新溶于CHCl3,并通过硅藻土塞过滤。去除溶剂得到产物。需要随后通过重结晶纯化。
实施例609 - 制备发射体104
按照实施例608,用5,7-二甲基-8-羟基喹啉作为R-OH。产率:66.4%。MS (FAB) m/z: 521.1 [M+] . 1H NMR (400 MHz, CDCl3): δ 9.04 (d, 1H, J = 4.88 Hz) , 8.52(d, 1H, J = 8.38 Hz) , 8.13 (d, 1H, J = 7.7 Hz) , 7.61 -7.64 (m, 1H) , 7.57(d, 1H, J = 7.67 Hz) , 7.44 (d, 1H, J = 7.50 Hz) , 7.36 -7.38 (m, 2H) , 7.21-7.25 (m, 2H) , 7.05 -7.13 (m, 2H) , 2.61 (s, 1H) , 2.59 (s, 1H) . 对C23H18AuNO计算的元素分析:C, 52.99; H, 3.48; N, 2.69。实验值:C, 52.91; H, 3.53;N, 2.80。
实施例609 - 制备发射体105
按照实施例608,用1-亚硝基萘-2-酚作为R-OH。产率:54.1%。MS (FAB) m/z:522.3 [M+] . 1H NMR (400 MHz, CDCl3): δ 9.35 (d, 1H, J = 8.32 Hz) , 8.20 (d,1H, J = 8.05 Hz) , 7.89 (d, 1H, J = 9.38 Hz) , 7.62 -7.72 (m, 3H) , 7.49 (t,1H, J = 7.43 Hz) , 7.31 (d, 2H, J = 7.48 Hz) , 7.17 -7.22 (m, 2H) , 7.07 -7.12 (m, 2H) , 7.00 (t, 1H, J = 7.46 Hz) . 对C22H14AuNO2计算的元素分析:C,50.69; H, 2.71; N, 2.69。实验值:C, 50.65; H, 2.74; N, 2.82。
实施例610 - 制备发射体106
按照实施例608,用2,4-二叔丁基-6-(二苯基膦基)苯酚作为R-OH。产率:47.1%。MS(FAB) m/z: 734 [M+] . 1H NMR (400 MHz, CDCl3): δ 8.23 (t, 1H, J =7.94 Hz) ,7.69 -7.74 (m, 4H) , 7.34 -7.54 (m, 9H) , 7.18 -7.24 (m , 3H) , 7.11 (t, 1H,J =7.49 Hz) , 6.89 (dd, 1H, J = 2.24 Hz; J = 10.4 Hz) , 6.69 (t, 1H, J = 7.52Hz) , 1.59 (s, 9H) , 1.22 (s, 9H) . 对C38H38AuOP计算的元素分析:C, 61.79; H,5.19。实验值:C, 61.75; H, 5.16。
实施例611 - 制备发射体107
使Na(acac) (12.2 mg, 0.1mmol)溶于最小量EtOH。加入10mL CHCl3。向混合物加入中间体422(50mg, 0.05mmol),并使温度升高到50℃。浑浊溶液快速变得较澄清。在加热过夜后,使溶剂在减压下蒸发。使粗物质重新溶于CHCl3,并通过硅藻土塞过滤。产物在MeOH中沉淀得到白色固体产物。产率:45mg (79.8%)。MS (FAB) m/z: 560.3 [M+] . 1H NMR(400 MHz, CDCl3): δ 7.70 (s, 2H) , 7.20 (s, 4H) , 5.51 (s, 1H) , 2.19 (s, 6H), 1.35 (s, 18H) . 对C25H31AuO2:C计算的元素分析:53.57; H, 5.57。实验值:C, 53.24;H, 5.59。
实施例612 - 制备发射体108
使K(OPPh2)2N (47mg, 0.10mmol)溶于最小量EtOH。加入10mL CHCl3。向混合物加入中间体422(50mg, 0.05mmol),使温度升高到50℃,并反应2h。将具有一些金属沉积物的无色溶液通过硅藻土塞过滤。然后在减压下蒸发溶剂。产物在MeOH中沉淀得到白色固体产物。在CHCl3/己烷中重结晶得到纯无色结晶。产率:73mg (82.6%)。MS (FAB) m/z: 878.5[M+] . 1H NMR (400 MHz, CDCl3): δ 7.86 -7.91 (m, 8H) , 7.78 (s, 2H) , 7.31 -7.41 (m, 12H) , 7.15 (s, 4H) , 1.34 (s, 18H) ; 31P NMR (CDCl3): δ 28.6. 对C44H44AuNO2P2计算的元素分析:C, 60.21; H, 5.05; N, 1.60。实验值:C, 60.08; H,5.07; N, 1.75。
实施例613 - 制备中间体109
使K2CO3粉末(22mg, 0.159mmol)悬浮于2mL EtOH。将其加到溶于10mL CHCl3的2-乙酰基-3-羟基苯并[b]噻吩(15.4mg, 0.080mmol)。将混合物加热到50℃经历10分钟,随后加入中间体422(40mg, 0.040mmol)。混合物在2h内变得澄清。然后在减压下蒸发溶剂。使粗物质重新溶于CHCl3,并通过硅藻土塞过滤。去除溶剂得到产物。在CHCl3/己烷混合物中重结晶得到纯黄色固体。产率:35mg (66.6%)。MS (FAB) m/z: 652.3 [M+] . 1H NMR (300 MHz,CDCl3): δ 8.08 (d, 1H, J = 7.86 Hz) , 7.96 (s, 1H) , 7.78 (s, 1H) , 7.66 (d,1H, J = 7.94 Hz) , 7.59 (t, 1H, J = 7.40 Hz) , 7.23 (s, 2H) , 7.22 (s, 2H) ,2.63 (s, 3H) , 1.44 (s, 9H) , 1.38 (s, 9H) . 对C30H31AuO2S计算的元素分析:55.21;H, 4.79。实验值:C, 55.19; H, 4.79。
实施例614 - 制备发射体110
使K2CO3粉末(17mg, 0.123mmol)悬浮于2mL EtOH。将其加到溶于THF的水杨醛(8mg, 0.065mmol)。将混合物加热到50℃经历10分钟,随后加入中间体422(30mg,0.030mmol)。混合物在2小时内变得澄清。然后在减压下蒸发溶剂。使粗物质重新溶于THF,并通过硅藻土塞过滤。通过MeOH在浓THF溶液中诱导沉淀得到黄色固体。产率:13mg(37.0%)。MS (FAB) m/z: 582.2 [M+] . 1H NMR (400 MHz, CDCl3): δ 9.47 (s, 1H) ,7.87 (s, 1H) , 7.70 (s, 1H) , 7.64 (t, 1H, J = 7.72 Hz) , 7.46 (d, 1H, J =8.20 Hz) , 7.19 -7.22 (m, 4H) , 7.05 (d, 1H, J = 8.80 Hz) , 6.72 (t, 1H, J =7.40 Hz) , 1.39 (s, 18H)。
实施例615 - 发射体102、104、107和109的相邻分子之间的平面间距和Au…Au距离汇总
发射体 | 平面间距/ Å | Au…Au距离/ Å |
102 | n/a | n/a |
104 | 3.36 | 4.3998(4) |
107 | 3.31 | 3.4083(4) |
109 | 约3.4 | 3.4530(5) |
实施例616 -发射体102、104、107和109的选择键长和键角
实施例617 -发射体102、104、107和109的晶体数据
ORETP图描绘于图201-图205中。
实施例618 -发射体101、102、103、105、107、108和109的电化学数据
循环伏安图描绘于图206中。
实施例619 - 发射体102、103和107的TGA数据
发射体 | 分解温度/℃ |
102 | 305 |
103 | 280 |
107 | 280 |
TGA温谱图描绘于图207-209中。
实施例619 - 发射体101和102的光物理数据
实施例620 - 发射体102的OLED制造
为了研究发射体102的电致发光(EL)性能,已研究通过真空沉积(VDOLED)和溶液方法(SPOLED)技术二者制造的有机发光装置(OLED)。考虑102的高三重态能量(Et~2.7eV),具有高于2.7eV的Et的基质和电荷传输材料对有效限制三重态激子在发射层(ETL)内和阻挡返回能量传递到基质和/或电荷传输材料是必要的。三重态激子的低效限制和返回能量传递严重降低装置效率。利用这种装置设计策略,已分别在VDOLED中用9-(4-叔丁基苯基)-3,6-双(三苯基甲硅烷基)-9H-咔唑(CzSi, Et=3.02eV)和4-(三苯基甲硅烷基)苯基二苯基氧化膦-(TSPO1, Et=3.36 eV)作为基质和电子传输/空穴阻挡层(ETL/HBL)。VDOLED的装置结构为ITO/MoO3 (2nm) /TAPC (40nm) /TCTA (10 nm) /CzSi (3 nm) /CzSi:102 (20nm) /TSPO1 (10 nm) /TPBi (40 nm) /LiF (1.2 nm) /Al (150 nm)。除了以上提到的CzSi和TSPO1外,用二-[4-(N,N-二甲苯基-氨基)-苯基]环己烷(TAPC)作为空穴传输层(HTL),用4,4′,4″-三(咔唑-9-基)三苯基胺(TCTA)作为空穴传输/电子阻挡层(HTL/EBL),用2,2',2"-(1,3,5-苯三基)-三(1-苯基-1-H-苯并咪唑)(TPBi)作为ETL。类似地,利用102作为发射掺杂剂,已在SPOLED中用高Et材料2,6-二咔唑-1,5-吡啶(PYD2, Et=2.93eV)和氧化双{2-[二(苯基)膦基]-苯基}醚(DEPEO, 3.00eV)分别作为基质和ETL/HBL。SPOLED的装置结构为ITO/PEDOT:PSS/PYD2:102 (40 nm) /DEPEO (5 nm) /TPBi (40 nm) /LiF (1.2nm) /Al (Al)。在VDOLED或SPOLED二者中,102的掺杂浓度为4%重量或10%重量。
实施例620 - 利用发射体102的OLED的关键性能参数
aOLED通过真空沉积制造。bOLED通过溶液方法制造。c起始电压(亮度=1cd m-2)。d在100cd m-2的CIE坐标。
VDOLED和SPOLED的EL光谱和EQE亮度特征描绘于图212和213中。
关于给定性质的任何数字或数值范围,来自一个范围的数字或参数可与来自相同性质不同范围的另一个数字或参数组合,以产生数值范围。
除了操作实施例外,或者另外指明,说明书和权利要求中使用的所有涉及成分的量、反应条件等的数字、数值和/或表达均应理解为在所有情况下受词语“约”修饰。
虽然已关于某些实施方案说明本发明,但应了解,通过阅读说明书,各种改进对本领域的技术人员显而易见。因此,应了解,本文公开的本发明旨在覆盖落在所附权利要求范围内的所有这些改进。
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KR102085190B1 (ko) | 2020-03-05 |
CN107849062A (zh) | 2018-03-27 |
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US10672999B2 (en) | 2020-06-02 |
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