CN110229192B - 一种氘代铱配合物及其制备方法和应用 - Google Patents
一种氘代铱配合物及其制备方法和应用 Download PDFInfo
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- CN110229192B CN110229192B CN201910548621.6A CN201910548621A CN110229192B CN 110229192 B CN110229192 B CN 110229192B CN 201910548621 A CN201910548621 A CN 201910548621A CN 110229192 B CN110229192 B CN 110229192B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一种氘代铱配合物及其制备方法,以及该化合物在电致发光材料方面的应用和相关光电物理性质。通过对环金属铱(III)配合物的有机配体修饰,可以提高发光材料分子的荧光量子效率(PLQE),提高配合物在发光过程中的稳定性,并且可以进一步增加材料器件应用的稳定性。据这些分子的光谱特征、电化学性能和化合物改造功能,很明确的这类分子可以用来制备高质量的OLED相关器件和应用器具。
Description
技术领域
本发明属于电子材料技术领域,具体涉及一种氘代铱配合物及其制备方法,以及该配合物在电致发光器具方面的应用。
背景技术
有机电致发光是指有机材料在受到电流和电场的激发后将电能转化为光能的发光过程,这种电致发光现象最早是在1963年美国New York大学的Pope教授发现的。相对于无机发光材料,有机发光材料可以更贴近对光适应性方面的需求。基于有机发光二极管(OLED)技术制造的显示器和发光器具有柔性外形,并且增加了诸多艺术元素于电子器件中。最早的有机电致发光器件由Eastman Kodak发展出来,通过芳香胺有机小分子作为空穴传输层,8-羟基喹啉铝作为发光层(“Organic electroluminescent diodes”Tang,Vanslyke等,ApplPhys Lett,第51卷,第913-915页,1987年)。这类以有机分子作为核心发光材料的器件称之为有机发光二极管(OLED),可以应用于新型显示和照明领域,具有诸多优点和潜力。有机材料制备的发光器件具有高量子效率、高亮度、高发光效率等优点;由有机发光材料制备成的发光设备外形上具有轻、薄、柔等优势,尤其可制备成柔性设备是其它发光材料无法与之相比的优点。根据核心的电致发光材料进行分类,传统的OLED可以分为荧光类OLED和磷光类OLED。与荧光OLED相比(理论发光效率最高25%),磷光OLED(理论发光效率100%)由于具有更高的发光效率而成为OLED技术研究和发展的主流方向。(“Highlyefficient phosphorescent emission fromorganic electroluminescent devices”M.A.Baldo*,D.F.O’Brien*,Y.You,A.Shoustikov,S.Sibley,M.E.Thompson&S.R.ForrestNature Vol 3951998 151-154)
激子从单重激发态到基态的衰减产生快速发光,即荧光。激子从三重激发态到基态的衰减产生光,即磷光。由于重金属原子的强自旋轨道耦合(ISC)能非常有效地增强单重激发态和三重激发态之间的电子自旋态交叉变化,磷光金属络合物,如铂络合物,已显示了它们收获单重和三重激发态两者以及达到100%内部量子效率的潜力。因此,磷光金属络合物是作为有机发光器件(OLED)发光层掺杂物的很好候选材料,它在学术和工业领域都以得到非常多的注意。并且在过去的十年中,人们已经在该技术走向高利润商业化的道路上取得了一定成果,例如,OLED已经在智能手机、电视机和数码相机的先进显示器中得到应用。
铱(Ⅲ)络合物是一类应用广泛的磷光材料,(“Synthesis and Characterizationof Phosphorescent Cyclometalated Iridium Complexes”Sergey Lamansky,PeterDjurovich,Drew Murphy,Feras Abdel-Razzaq,Raymond Kwong,Irina Tsyba,ManfredBortz,Becky Mui,Robert Bau,and Mark E.Thompson Inorganic Chemistry,2001Vol.40,No.7,1704-1711)尽管上述有机发光材料在制造OLED面板和照明器具方面已经商业化,然而这些材料仍然有很多提升空间,比如降低材料制备工艺成本、提高材料的基本光电性能、提升最终产品应用感受质量、减少器件制程中材料配套成本,以及提高材料在器件集成后整体耐受性和耐候性等方面。
现有技术中,(WO2015039723)公开了多环苯基吡啶的铱配合物的合成及其在有机光电器件中的应用;US20030072964、US20070087321公开了苯基异喹啉为配体的有机磷光材料;US20080261076公开了2-喹啉苯基和2-异喹啉苯基为配体的Ir的杂配络合物用作有机磷光材料;US20120181511公开了5-取代的苯基喹啉的铱配合物在发光二极管中的应用,其中有涉及二酮结构辅助配体苯基吡啶;CN107459535A公开了3、4或者5位单取代的苯基吡啶的铱配合物的合成及其在有机光电器件中的应用,其制备方法包括了3,4位取代,3,5位取代,4,5位取代和3,4,5位取代的喹啉配体配位的化合物,辅助配体为二酮结构。WO2013094620公开了多取代吡嗪配体配位的Ir的杂配络合物用作有机磷光红光材料;Deep-red iridiumcomplexes cyclometalated by phenanthridine derivatives forhighly efficient solution-processed organic light-emitting diodesBei Jiang,YuGu,Jingjing Qin,Xiaowen Ning,Shaolong Gong,Guohua Xie和Chuluo Yang Journal ofMaterials Chemistry C 2016page 3492-3498报道了苯基菲啶配体配位的Ir杂配磷光材料;Highly efficient,deep-red organic light-emitting devices using energytransfer from exciplexes Yuji Nagai,Hisahiro Sasabe,Jun Takahashi,a NatsukiOnuma,Takashi Ito,a Satoru Ohisaab和Junji Kido报道了苯基喹喔啉配位的Ir的杂配化合物在深红光到近红外材料中的应用。US20080217606有公开过苯基喹啉为配体,吡啶咪唑和苯基吡啶咪唑为辅助配体的有机发光二极管材料,其内容仅限于简单取代的苯基喹啉配体;US20080261076有公开过苯基异喹啉为配体,吡啶咪唑和苯基吡啶咪唑为辅助配体的有机发光二极管材料。同位素取代可以提高材料在应用中的性能,论文Synthesis of all-deuterated tris(2-phenylpyridine)iridium for highly stableelectrophosphorescence:the“deuterium effect”Ping Wang,Fei-Fei Wang,Yi Chen,Qiang Niu,Lei Lu,Hong-Ming Wang,Xi-Cun Gao,Bin Wei,Hong-Wei Wu,Xin Caic andDe-Chun ZouJ.Mater.Chem.C,2013,1,4821–4825公开报道了氘代的三苯基吡啶铱配合物具有更稳定的电致发光效果。专利CN107200755公开了氘代配合物提高磷光发光材料性能的方案。其中,二酮结构辅助配体配位的铱配合物用作有机发光材料具有非常好的经济适用性和工艺可操作性,相对研究较多。其中对于辅助配体配位的铱配合物在OLED器件应用中失活机理的研究(Chemical Degradation in Organic Light-EmittingDevices:Mechanisms and Implications for the Design of New Materials,SusannaSchmidbauer,Andreas Hohenleutner and Burkhard Adv.Mater.2013,25,2114–2129)报道了辅助配体要比其它主配体易于解离并导致铱配合物光电功能材料分子失活。专利CN108299510公开了辅助配体的替代配体方案。
发明内容
本发明所要解决的技术问题是:公开了一种氘取代的有机金属配合物及其制备方法,以及该化合物在电致发光材料方面提升性能的相关应用。
为了解决上述技术问题,本发明所采用的技术方案是:
提供一种氘代铱配合物,具有以下分子结构式:
其中Ra、Rb为独立存在的氢原子、烷基取代基和芳基取代基,烷基取代基可以氘代的、部分氘代的和芳基取代的烷基,芳基取代基可以是氘代的、部分氘代的和含有烷基或芳基取代基的芳基;Rc是非氘代的烷基取代基。
其中,所述烷基为直链或者支链的含有2-6个碳原子的烷基,可以包括乙基、正丙基、异丙基、正丁基、异丁基、特丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、2,3-二甲基丙基和1-乙基丙基、环戊基、环己基、2-甲基-3-戊基、3,3-二甲基-2-丁基。
所述氘代铱配合物为铱配合物Ir-2、Ir-16、Ir-23、Ir-62和Ir-71,具体结构式为分子结构式如下:
所述氘代铱配合物的制备方法,至少包括以下步骤:(1)将前体物质与三价铱反应制备得到二聚物;(2)所述二聚物与辅助配体前体化合物和氘代试剂通过一步反应或者两步反应,得到所述分子式I所示化合物;化学反应方程式如下所示:
所述氘代试剂包括氘水、氘代DMSO、氘代甲醇、氘代乙醇、氘代乙酸、氘代甲酸、氘代甲酸钠、氘代苯、氘代DMF。
此外,本发明还提供了一类含有氘代铱配合物在电致发光材料方面的应用,具体可以用于有机电子组件,例如有机电子组件,其为有机发光二极管、发光二极管、紧凑型荧光灯、白炽灯、有机光伏电池、有机场效应晶体管或发光电化学电池。尤其是有机光电发光器件,还可以作为生物标记或在成像技术中应用。
本发明的有益效果是:与现有技术相比,本发明公开了一种新型电致发光材料,在主配体中特定位点引入提升了化合物的稳定性,该类化合物具有至少保持原有配合物(未被氘代的)高效的光电转化特性,在光、电、热稳定性方面都有提升,作为掺杂发光材料应用于电致发光器件相关的器具用可以提高器具的使用寿命。其中涉及的制备路径和方法在制备含有氘代二酮辅助配体的铱配合物上具有通用性、高效性和量产成本适合等优点。据这些分子的光谱特征和化合物改造功能,很明确的这类分子可以用来制备高质量的有机电致发光的相关器件和应用器具。
附图说明
图1为使用本发明所述氘代二酮辅助配体的铱配合物作为致电发光材料的OLED结构图;
图2为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm光致发光光谱对比图;
图3为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备成器件的发光光谱图;
图4为常温下氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备的OLED器件的发光图(4a)和电压亮度变化图(4b);
图5为常温下氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备的OLED器件的的发光电流效率图(5a)和功率效率图(5b);
图6氘代铱配合物Ir-23的核磁氢谱与非氘代产物对比图;
图7氘代铱配合物Ir-62结构表征的核磁氢谱;
图8氘代铱配合物Ir-17结构表征的核磁氢谱;
图9氘代铱配合物Ir-71结构表征的核磁氢谱;
图10氘代铱配合物Ir-62的超高压高效液相分析纯度和匹配质谱检测图;
图11氘代铱配合物Ir-17的质谱检测图。图例说明Ir-17为氘代产物;
图12氘代铱配合物Ir-71的质谱检测图。图例说明Ir-71为氘代产物。
图13为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备成OLED器件后的光致发光随时间的衰减曲线;
图14为氘代铱配合物Ir-65和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm制备的器件发光致随时间的衰减曲线;
图15为氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm制备的OLED寿命测试图。
具体实施方式
本发明所采用的技术方案是:提供一种适合工艺制备的稳定性更好的氘代铱配合物,具有以下分子结构式:
其中Ra、Rb为独立存在的氢原子、烷基取代基和芳基取代基,烷基取代基可以氘代的、部分氘代的和芳基取代的烷基,芳基取代基可以是氘代的、部分氘代的和含有烷基或芳基取代基的芳基。Rc是烷基取代基。烷基取代基可以氘代的、部分氘代的和芳基取代的烷基。
本文烷基指直链或者支链的含有2-6个碳原子,这类烷基可以包括乙基、正丙基、异丙基、正丁基、异丁基、特丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、2,3-二甲基丙基和1-乙基丙基、环戊基、环己基、2-甲基-3-戊基、3,3-二甲基-2-丁基等。
分子式I可以是以下分子Ir-1至Ir-90,但不局限于分子Ir-1至Ir-90,分子Ir(pq)2acac、Ir(dmpiq)2divm为常规磷光发光分子,化学结构式如下图,其中Ir(dmpiq)2divm为铱配合物Ir-62的非氘代产物。
实施例1.氘代铱配合物Ir-62的合成和结构表征
二聚体A的合成。向75ml封管中加入1-(3,5-二甲基苯基)异喹啉(1.1g,4.7mmol),三水三氯化铱(332.6mg,0.9mmol),乙二醇***(15mL)和水(5mL),氮气置换反应瓶氛围。将反应体系加热至100℃,搅拌12小时。将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体A(660mg,45%)。
铱配合物62(Ir-62)前体的合成。向15ml封管中加入二聚体A(72.2mg,0.05mmol),2,8-二甲基壬烷-4,6-二酮(0.1ml),碳酸钠(26.5mg,0.25mmol)和乙二醇***(3mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得铱配合物62前体(60mg,69%)。1H NMR(300MHz,DMSO)δ8.92-8.89(m,2H),8.10(d,J=6.3Hz,2H),8.02-7.99(m,2H),7.92(s,2H),7.81–7.78(m,4H),7.52(d,J=6.3Hz,2H),6.45(s,2H),4.82(s,1H),2.29(s,6H),1.71–1.67(m,2H),1.56–1.49(m,2H),1.32(s,6H),1.25-1.13(m,2H),0.31(d,J=6.6Hz,6H),-0.18(d,J=6.6Hz,6H).MS(ESI):841.4[M+1]+
氘代铱配合物Ir-62的合成。向15ml封管中加入铱配合物62前体(84.0mg,0.1mmol),碳酸钠(26.5mg,0.25mmol),乙二醇***(3mL)和重水(0.1mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得氘代铱配合物Ir-62(63mg,75%)。图7为氘代铱配合物Ir-62结构表征的核磁氢谱。1HNMR(300MHz,CDCl3)δ8.99-8.96(m,2H),8.24(d,J=6.3Hz,2H),7.97(s,2H),7.83-7.79(m,2H),7.71-7.63(m,4H),7.23(d,J=6.6Hz,2H),6.58(s,2H),4.80(s,0.06H),2.34(s,6H),1.82-1.76(m,2H),1.54-1.50(m,2H),1.45(s,6H),1.29(m,0H),0.33(d,J=6.6Hz,6H),-0.13(d,J=6.6Hz,6H).MS(ESI):842.4[M+1]+Emission peak in DCM at 625nm,FWHM=59nm,peak in PMMA at 629nm,FWHM=54nm。图10为氘代铱配合物Ir-62的超高压高效液相分析纯度和匹配质谱检测图。图10说明,氘取代后的化合物Ir-62可以很好的提纯,且稳定性好,适合量产工艺控制,最终得到高纯的电子级纯度的有机光电材料化学品。
实施例2:氘代Ir-71合成和结构表征
二聚体B的合成。向75ml封管中加入1-(3,5-二甲基苯基)-6-异叔丁基异喹啉(1.16g,4.0mmol),三水三氯化铱(282.6mg,0.8mmol),乙二醇***(15mL)和水(5mL),氮气置换反应瓶氛围。将反应体系加热至100℃,搅拌12小时。将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体B(720mg,45%)。
铱配合物71前体的合成。向15ml封管中加入二聚体B(160.7mg,0.1mmol),2,8-二甲基壬烷-4,6-二酮(0.1ml),碳酸钠(53mg,0.5mmol)和乙二醇***(3mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得铱配合物71前体(90mg,69%)。1H NMR(500MHz,CDCl3)δ8.88(d,J=9.0Hz,2H),8.20(d,J=6.5Hz,2H),7.97(s,2H),7.54(s,2H),7.49(d,J=9.0Hz,2H),7.16(d,J=6.5Hz,2H),6.57(s,2H),4.79(s,1H),2.70(d,J=7.0Hz,4H),2.34(s,6H),2.07-2.04(m,2H),1.87-1.77(m,2H),1.54-1.52(m,2H),1.46(s,6H),1.33-1.30(m,2H),1.01-0.99(m,12H),0.33(d,J=7.0Hz,6H),-0.11(d,J=6.5Hz,6H).MS(ESI):953.6[M+1]
氘代铱配合物71的合成。向15ml封管中加入铱配合物71前体(95.3mg,0.1mmol),碳酸钠(53mg,0.5mmol),乙二醇***(3mL)和重水(0.2mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得氘代铱配合物71(70mg,73%)。图9为氘代铱配合物Ir-71结构表征的核磁氢谱。1H NMR(500MHz,CDCl3)δ8.88(d,J=8.5Hz,0H),8.20(d,J=6.5Hz,2H),7.97(s,2H),7.54(s,2H),7.49(d,J=8.5Hz,2H),7.16(d,J=6.5Hz,2H),6.57(s,2H),2.71(d,J=7.0Hz,4H),2.34(s,6H),2.08-2.03(m,2H),1.80-1.77(m,2H),1.53-1.51(m,2H),1.46(s,6H),1.34-1.30(m,2H),1.01-0.99(m,2H),0.33(d,J=7.0Hz,6H),-0.11(d,J=6.5Hz,6H).MS(ESI):954.4[M+1]+Emission peak in DCM at 619nm,FWHM=58nm,peak in PMMA at 622nm,FWHM=53nm。图12氘代铱配合物Ir-71的质谱检测图,图例说明Ir-71为氘代产物。
实施例3:氘代Ir-23合成和结构表征
二聚体C的合成。向75ml封管中加入1-(3,5-二甲基苯基)-6-异丙基异喹啉(1.10g,4.0mmol),三水三氯化铱(282.6mg,0.8mmol),乙二醇***(15mL)和水(5mL),氮气置换反应瓶氛围。将反应体系加热至100℃,搅拌12小时。将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体C(700mg,45%)。
铱配合物Ir-23前体的合成。向15ml封管中加入二聚体C(155.1mg,0.1mmol),3,7-二乙基-4,6-二酮(0.1ml),碳酸钠(26.5mg,0.25mmol)和乙二醇***(3mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,旋干过柱(石油醚:乙酸乙酯=10:1)得红色铱配合物Ir-23前体(110mg,58%)。1H NMR(500MHz,CDCl3)δ8.89(d,J=8.5Hz,2H),8.16(d,J=6.5Hz,2H),7.94(s,2H),7.58(s,2H),7.55(d,J=9.0Hz,2H),7.11(d,J=6.0Hz,2H),6.56(s,2H),4.80(s,1H),3.14-3.08(m,2H),2.33(s,6H),1.43(s,6H),1.38-1.36(m,12H),1.30-1.24(m,4H),1.11-1.05(m,2H),0.90-0.81(m,4H),0.42(t,J=7.5Hz,6H),-0.16(t,J=7.3Hz,6H).MS(ESI):953.4[M]+
氘代铱配合物Ir-23的合成。向15ml封管中加入铱配合物Ir-23前体(95.2mg,0.1mmol),碳酸钠(53mg,0.5mmol),乙二醇***(3mL)和重水(0.2mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得氘代铱配合物Ir-23(80mg,84%)。1H NMR(500MHz,CDCl3)δ8.89(d,J=9.0Hz,2H),8.16(d,J=6.0Hz,2H),7.94(s,2H),7.58(s,2H),7.56(d,J=9.0Hz,2H),7.11(d,J=6.0Hz,2H),6.56(s,2H),4.80(s,1H),3.15-3.09(m,2H),2.35(s,6H),1.45(s,6H),1.40-1.38(m,12H),1.31-1.25(m,4H),1.12-1.07(m,2H),0.92-0.82(m,4H),0.42(t,J=7.6Hz,6H),-0.16(t,J=7.5Hz,6H).MS(ESI):954.4[M+1]+Emission peak in DCM at 620nm,FWHM=58nm,peak in PMMA at 621nm,FWHM=51nm。图6氘代铱配合物Ir-23的核磁氢谱与非氘代产物对比图。图示表明采用本发明提供的方法,可以将指定位置的氢(H)原子转换成相应的单一同位素氘(D)原子,最终产品的氘代率大于99%。
实施例4:氘代Ir-17合成和结构表征
铱配合物Ir-17前体的合成。向15ml封管中加入二聚体A(134.4mg,0.1mmol),3,7-二乙基-4,6-二酮(0.1ml),碳酸钠(53mg,0.5mmol)和乙二醇***(3mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,旋干过柱(石油醚:乙酸乙酯=10:1)得红色铱配合物Ir-17前体(140mg,80%)。1H NMR(500MHz,CDCl3)δ8.98(d,J=8.0Hz,2H),8.22(d,J=6.5Hz,2H),7.97(s,2H),7.80-7.79(m,2H),7.68-7.63(m,4H),7.17(d,J=6.0Hz,2H),6.58(s,2H),4.82(s,1H),2.36(s,6H),1.60-1.53(m,2H),1.45(s,6H),1.32-1.26(m,2H),1.13-1.08(m,2H),0.91-0.84(m,4H),0.44(t,J=7.5Hz,6H),-0.15(t,J=7.5Hz,6H).MS(ESI):869.4[M+1]+
氘代铱配合物Ir-17的合成。向15ml封管中加入铱配合物Ir-17前体铱配合物(86.9mg,0.1mmol),碳酸钠(53mg,0.5mmol),乙二醇***(3mL)和重水(0.2mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得氘代铱配合物Ir-17(75mg,86%)。图8为氘代铱配合物Ir-17结构表征的核磁氢谱。1H NMR(500MHz,CDCl3)δ8.98(d,J=8.0Hz,2H),8.22(d,J=6.0Hz,2H),7.97(s,2H),7.80-7.79(m,2H),7.68-7.63(m,4H),7.17(d,J=6.0Hz,2H),6.58(s,2H),4.82(s,0.09H),2.36(s,6H),1.60-1.55(m,2H),1.45(s,6H),1.32-1.26(m,2H),1.13-1.08(m,2H),0.91-0.84(m,4H),0.44(t,J=7.5Hz,6H),-0.14(t,J=7.5Hz,6H).MS(ESI):870.4[M+1]+Emission peak in DCM at 626nm,FWHM=57nm,peak in PMMA at 626nm,FWHM=50nm。图11为氘代铱配合物Ir-17的质谱检测图,图例说明Ir-17为氘代产物。
实施例5:氘代Ir-2合成和结构表征
铱配合物Ir-2前体的合成。向15ml封管中加入二聚体A(134.4mg,0.1mmol),3,7-二甲基-4,6-二酮(0.1ml),碳酸钠(53mg,0.5mmol),乙二醇***(3mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,旋干过柱(石油醚:乙酸乙酯=10:1)得红色铱配合物Ir-2前体(130mg,77%)。1H NMR(500MHz,CDCl3)δ8.99(d,J=7.0Hz,2H),8.20-8.16(m,2H),7.96(s,2H),7.80(d,J=8.0Hz,2H),7.67-7.63(m,4H),7.18(d,J=6.0Hz,2H),6.59(s,2H),4.79(t,J=6.0Hz,1H),2.36(s,6H),1.81-1.74(m,2H),1.47(s,6H),1.23-1.19(m,1H),1.02-0.97(m,1H),0.88-0.84(m,1H),0.78-0.77(m,3H),0.75-0.70(m,1H),0.37-0.32(m,6H),-0.17--0.21(m,3H).MS(ESI):841.4[M+1]
氘代铱配合物Ir-2的合成。向15ml封管中加入铱配合物Ir-2前体(84.4mg,0.1mmol),碳酸钠(53mg,0.5mmol),乙二醇***(3mL)和重水(0.2mL),氮气鼓泡三分钟,反应体系加热回流12小时。将反应液冷至室温,过滤,滤液旋干过柱(石油醚:乙酸乙酯=10:1)得氘代铱配合物Ir-2(70mg,83%)。1H NMR(500MHz,CDCl3)δ8.99(d,J=7.0Hz,2H),8.20-8.17(m,2H),7.96(s,2H),7.80(d,J=7.5Hz,2H),7.69-7.63(m,4H),7.18(d,J=6.5Hz,2H),6.58(s,2H),2.36(s,6H),1.81-1.74(m,2H),1.47(s,6H),1.23-1.19(m,1H),1.03-0.97(m,1H),0.90-0.82(m,1H),0.77(d,J=7.0Hz,3H),0.74-0.70(m,1H),0.37-0.32(m,6H),-0.17--0.21(m,3H).MS(ESI):842.4[M+1]+Emission peak in DCM at 627nm,FWHM=60nm,peak in PMMA at 627nm,FWHM=52nm。
实施例6氘代铱配合物材料表征测试
对本发明所述氘代铱配合物的光学性质进行比较,测试方法如下:材料的带隙值(Eg)和LUMO值采用循环伏安法(CV)测得。整个测试过程在手套箱(Lab2000,Etelux)中的CHI600D电化学工作站(上海辰华仪器公司)上进行,以Pt柱为工作电极、以Ag/AgCl为参比电极,Pt丝为辅助电极构成三电极***,测试过程采用的介质是0.1M六氟磷酸四丁基胺(Bu4NPF6)的二甲基二酰胺(DMF)溶液,所测电势均以加入的二茂铁(Fc)作为内标。材料的HOMO值通过Model IPS-4Ionization Energy Measurement System直接测试得到。材料的荧光量子效率(PLQE)依据公式(其中:Φs是样品的荧光量子产率,Φr是标样的荧光量子产率,η是溶液的折射率,As和Ar是样品和标样的荧光激发波长处的吸收值,Ιs和Ιr是样品和标样的荧光积分面积)采用相对法计算得到。将材料和已知量子产率的标物配置成相同浓度的聚甲基丙烯酸甲酯(PMMA)的三氯甲烷溶液,旋涂成膜,在相同的测量条件下,测得紫外吸收光谱(GENESYS 10S,Thermo)和荧光光谱(F97pro荧光分光光度计,棱光科技)。材料的光子能量(ET1)由公式E=hν=1240/λ(其中λ为材料PMMA膜的荧光光谱起始位置的切线波长)计算而来。从下表1可以看出,氘代铱配合物材料与非氘代铱配合物相比,荧光量子效率均有所提升。
表1
a通过循环伏安计测得b三线态的能量c PLQE效率以Ir(PQ)2(acac)在298K下的发光效率为基准值一个单位。
实施例7
将氘代铱配合物作为发光材料掺杂到主体材料中制备成器件OLED,其OLED器件结构如图1所示。其中Cathode为阴极、EIL为电子注入层、ETL为电子传输层、HTL为空穴传输层、HIL为空穴注入层、ITO为氧化铟电极。氘代二酮辅助配体配位的铱配合物Ir-62作为致电发光材料包含在EML(发光层中),发光层包括有主体材料和发光材料。将氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm应用于器件后的比较其发光性能等参数。
其中,图2为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm光致发光光谱对比图。由图2可知,两种材料发光光谱完全一致,荧光光谱均在红光区域可以制备成饱和红光器件。
图3为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备成OLED器件后的发光光谱图。如图3所示相同结构下的OLED在相同测试条件下的发光光谱型貌基本一致,但是发光强度有所区别,其中含有氘代产物Ir-62的OLED在相同的条件下具有更高的电致发光强度,光谱波长在625nm,较其在PMMA中的峰值红移。
图4为常温下氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备的OLED器件的发光图(J-V)和电压亮度变化图(V-L),相同结构下的器件在相同测试条件下的电流电压曲线基本一致,电压亮度曲线显示Ir-62对应的器件在相同电压下亮度更高。启动电压在3V以下,说明其核心发光材料具有非常好的发光性能以及在发光过程中的稳定性。
图5为常温下氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备的OLED器件的的发光电流效率图(5a)和功率效率图(5b)。由图中可知,氘代铱配合物Ir-62制备的OLED器件的具有更高电流效率>24cd/A、更高发光效率>25cd/W。
图13为氘代配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm用作红光掺杂材料制备成OLED器件后的光致发光随时间的衰减曲线。本次衰减测试是通过0.3mW/m2的紫外光照射掺杂5%的铱配合物的稳定聚苯乙烯高分子薄膜,并记录光致发光的强度,最终得到化合物发光衰减和时间的函数关系。图13显示,氘代后的配合物Ir-62发光强度保持要明显高于其非氘代材料Ir(dmpiq)2divm,其光致发光衰减的更慢,具有更好的光学稳定性。光照400分钟后,发光强度保留程度较非氘代材料高7-8%。
图14氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm制备的器件光致发光随时间的衰减曲线。器件结构为ITO/HT17:H09(5%,10nm)/HT17(150nm)/PH315:RD(2%,20nm)/ET15(60nm)/E02(2nm)/Al(120nm),其中RD代表Ir-62和对比的相同结构的非氘代铱配合物Ir(dmpiq)2divm。电致发光衰减测试的起始电流密度是50mA/cm2。图例显示,氘代后的材料Ir-62器件的衰减速度要明显低于其非氘代材料Ir(dmpiq)2divm,其电致发光衰减的更慢,具有更好的器件稳定性。LT97@50mA/cm2的寿命分别为78.6小时和30.9小时,氘代二酮辅助配体配位的材料Ir-62制备的器件明显优非氘代常规材料。
图15为氘代铱配合物Ir-62和非氘代二酮辅助配体的铱配合物Ir(dmpiq)2divm制备的OLED寿命测试图,寿命测试使用上海大学发光与光电研究室ZJLS-4型寿命测试仪,以恒流方式驱动实时测试OLED器件寿命。在本实验中,在恒定电流密度(50mA·cm-2)下测得器件亮度和电压随时间的变化曲线。图15A所示测试结果可以看出,氘代铱配合化合物制备的OLED器件稳定性更好,随着时间的变化,其亮度衰减较非氘代铱配合化合物慢;由图15B可知,氘代铱配合化合物制备的OLED器件,随着时间的变化,其电压升高幅度较非氘代铱配合化合物慢,没有升高说明器件没有衰减发生,升高幅度越大说明器件效果越差。因此,氘代材料的器件具有更低的电压变化,使用效果更好。
实施例8
将氘代铱配合物和非氘代二酮辅助配体的铱配合物制备成器件,并对其相关数据进行测试,其数据对比测试结果如下表2所示:
表2
如表2所示,通过器件数据对比可以看出,器件电致发光波长主要由Ir配合物本身光致发光的决定,在同一条件下,器件的效率高低也与Ir配合物本身的PLQE趋势一致。因此,本发明所公开的高PLQE的氘代铱配化合物可以在其它器件中获得高的器件效率。氘代铱配化合物和非氘代配化合物相比,部分产物电流效率(CE)和外量子效率(EQE)有明显的提高,如Ir-2和Ir-62;部分产物效率氘代前后没有明显的变化,如Ir-23;氘代铱配化合物和非氘代配化合物相比,所有器件的寿命均有明显的提高,提高幅度在15―30%之间,说明氘代铱配化合物作为发光材料用于制作OLED器件及其相关设备相比较其常规非氘代的铱配化合物具有明显的提高使用寿命的优势;
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (4)
2.一种合成如权利要求1所述氘代铱配合物Ir-2、Ir-16、Ir-23、Ir-62和Ir-71的方法,其合成路径分别如下:
氘代铱配合物62的合成方法:
(1)二聚体A的合成,向75ml封管中加入1-(3,5-二甲基苯基)异喹啉,三水三氯化铱,乙二醇***和水,氮气置换反应瓶氛围,将反应体系加热,搅拌,将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体A;
(2)铱配合物62前体的合成,向封管中加入二聚体A,2,8-二甲基壬烷-4,6-二酮,碳酸钠和乙二醇***,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得铱配合物62;
(3)氘代铱配合物Ir-62的合成,向封管中加入铱配合物62,碳酸钠,乙二醇***和重水,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得氘代铱配合物Ir-62;
氘代Ir-71合成方法:
(1)二聚体B的合成,向封管中加入1-(3,5-二甲基苯基)-6-异叔丁基异喹啉,三水三氯化铱,乙二醇***和水,氮气置换反应瓶氛围,将反应体系加热,搅拌,将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体B;
(2)铱配合物71前体的合成,向封管中加入二聚体B,2,8-二甲基壬烷-4,6-二酮,碳酸钠和乙二醇***,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得铱配合物71前体;
(3)氘代铱配合物71的合成,向封管中加入铱配合物71前体,碳酸钠,乙二醇***和重水,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得氘代铱配合物71;
氘代Ir-23合成方法
(1)二聚体C的合成,向封管中加入1-(3,5-二甲基苯基)-6-异丙基异喹啉,三水三氯化铱,乙二醇***和水,氮气置换反应瓶氛围,将反应体系加热,搅拌,将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体C;
(2)铱配合物Ir-23前体的合成,向封管中加入二聚体C,3,7-二乙基-4,6-二酮,碳酸钠和乙二醇***,氮气鼓泡,反应体系加热回流,将反应液冷至室温,旋干过柱得铱配合物Ir-23前体;
(3)氘代铱配合物Ir-23的合成,向封管中加入铱配合物Ir-23前体,碳酸钠,乙二醇***和重水,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得氘代铱配合物Ir-23;
氘代Ir-17合成方法:
(1)二聚体A的合成,向75ml封管中加入1-(3,5-二甲基苯基)异喹啉,三水三氯化铱,乙二醇***和水,氮气置换反应瓶氛围,将反应体系加热,搅拌,将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体A(2)铱配合物Ir-17前体的合成,向封管中加入二聚体A,3,7-二乙基-4,6-二酮,碳酸钠和乙二醇***,氮气鼓泡,反应体系加热回流,将反应液冷至室温,旋干过柱得铱配合物Ir-17前体;
(3)氘代铱配合物Ir-17的合成,向封管中加入铱配合物Ir-17前体,碳酸钠,乙二醇***和重水,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得氘代铱配合物Ir-17;
氘代Ir-2合成方法:
(1)二聚体A的合成,向75ml封管中加入1-(3,5-二甲基苯基)异喹啉,三水三氯化铱,乙二醇***和水,氮气置换反应瓶氛围,将反应体系加热,搅拌,将反应液冷至室温,固体析出,水洗,***洗涤,干燥得到二聚体A(2)铱配合物Ir-2前体的合成,向封管中加入二聚体A,3,7-二甲基-4,6-二酮,碳酸钠,乙二醇***,氮气鼓泡,反应体系加热回流,将反应液冷至室温,旋干过柱铱配合物Ir-2前体;
(3)氘代铱配合物Ir-2的合成,向封管中加入铱配合物Ir-2前体,碳酸钠,乙二醇***和重水,氮气鼓泡,反应体系加热回流,将反应液冷至室温,过滤,滤液旋干过柱得氘代铱配合物Ir-2。
3.权利要求1所述氘代铱配合物在电致发光材料方面的应用。
4.权利要求1所述氘代铱配合物作为电致发光材料在光电电器中的应用。
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